JP5369736B2 - Electrophotographic photosensitive member, electrophotographic photosensitive member cartridge and image forming apparatus containing novel enamine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor containing a low molecular weight enamine compound excellent in charge transport performance, showing relatively preferable electric characteristics and less causing cleaning failure, filming, contamination, afterimage (ghost), density decrease or the like in repeated use. <P>SOLUTION: The electrophotographic photoreceptor has a photosensitive layer on a conductive support, wherein the photosensitive layer contains at least one specified enamine compound. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an electrophotographic photosensitive member containing an enamine skeleton that can be suitably used as a photoconductive material for an electrophotographic photosensitive member in a photosensitive layer, an electrophotographic cartridge using the electrophotographic photosensitive member, and an image forming apparatus.

The electrophotographic technique is widely used in the fields of copiers, various printers, printing machines, etc. because it is excellent in immediacy and provides high-quality images. As an electrophotographic photoreceptor that is the core of electrophotographic technology, an electrophotographic photoreceptor using an organic photoconductive material (hereinafter simply referred to as “photosensitive material”) that has advantages such as non-pollution, easy film formation, and easy manufacture. Also referred to as "body").
In recent years, the use of image forming apparatuses such as electrophotographic copying machines has been expanded, and the market demand for image quality has been increasing. In particular, in office documents, in addition to the development of mapping technology and latent image forming technology for input, the types of character hieroglyphics are more abundant and finer at the time of output. Due to the spread and development, the reproducibility of a latent image with extremely high image quality that has few defects and unclearness in printed images is required.

  Furthermore, it is a common recognition in the industry that with the recent high performance and low cost of electrophotographic equipment, it is essential to increase the sensitivity of the electrophotographic photosensitive member and reduce the cost of the original material. Of these, in order to achieve high sensitivity, it is necessary not only to optimize the charge generation material, but also to develop a charge transport material with a good matching with it. It is necessary to develop charge transport materials that can be purified by reaction routes and simple purification steps. For this reason, high performance of charge transport materials having a low molecular weight has been attracting attention. The low molecular weight organic photoconductive material has the advantage of low production cost, and the physical properties or electrophotographic characteristics of the coating can be controlled by selecting the type and composition ratio of the binder to be used together. This is preferable because it is relatively easy. However, it has a drawback that the charge mobility is not so high.

As a conventional technique in which charge mobility is relatively excellent, a high molecular weight enamine compound can be used as a charge transport material. For example, it has been proposed that the enamine compounds described in Patent Documents 1 and 2 can be used as charge transport materials.
However, the compound group described in Patent Document 1 or 2 has relatively good electrical characteristics and mobility, while being mounted on an electrophotographic apparatus and repeatedly used, such as blade reversal and generation of rubbing noise. The problem was easy to happen. This problem is particularly remarkable when a suspension polymerization toner having a large circularity is used. In addition, these compound groups have a relatively high production cost and are disadvantageous economically.

  As described above, there is almost no low molecular weight organic compound having practically favorable characteristics for producing a photoreceptor.

Japanese Patent Laid-Open No. 11-149169 JP2003-215824

  The present invention has been made in view of the current situation, and the object thereof is to contain a low molecular weight enamine compound excellent in charge transporting ability, and have relatively good electrical characteristics. An object of the present invention is to provide an electrophotographic photosensitive member with less filming, dirt, afterimage (ghost), density reduction and the like. The present invention also provides an electrophotographic cartridge and an image forming apparatus that do not generate blade reversal and rubbing noise during printing, and an enamine compound that exhibits the excellent performance performance, using this electrophotographic photosensitive member. is there.

As the amine skeleton of a low molecular weight enamine compound, the present inventors have a substituent constant σp according to Hammett's rule of 0.20 or less, a benzene ring substituted with an organic group having 1 to 6 carbon atoms, or a commercially available condensed poly. By optimizing substituents in cyclic hydrocarbon compounds and introducing them as partial structures of enamine compounds, properties such as photosensitivity, residual potential, and charge mobility are improved relatively well and used for electrophotographic photoreceptors. In this case, it is possible to provide an electrophotographic photosensitive member with little cleaning failure, filming, dirt, afterimage (ghost), density reduction, etc., and by using this electrophotographic photosensitive member, blade reversal at the time of printing The present inventors have found that an electrophotographic cartridge and an image forming apparatus that do not generate rubbing noise can be provided, and have completed the present invention.
That is, the first gist of the present invention is an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains at least one enamine compound represented by the general formula [I]. The present invention resides in an electrophotographic photosensitive member.

(In the formula [1], R is the same or different, and the substituent constant σp in Hammett's rule is 0.20 or less, represents an organic group having 1 to 6 carbon atoms, and m represents an integer of 0 to 5. Ar ¹ has a substituent constant σp in the Hammett rule of 0.20 or less and a phenyl group having at least one organic group having 1 to 6 carbon atoms, or a substituent constant σp in the Hammett rule of 0.20 or less, A condensed polycyclic hydrocarbon group which may have an organic group of 1 to 6. Ar ² has a substituent constant σp in the Hammett rule of 0.20 or less, and an organic group of 1 to 6 carbon atoms R ¹ represents an alkyl group having 1 to 4 carbon atoms and may form a ring with Ar ^2. )
The second gist of the present invention is that the electrophotographic photosensitive member of the present invention, a charging means for charging the electrophotographic photosensitive member, and exposing the image to the charged electrophotographic photosensitive member to form an electrostatic latent image. Image exposing means, developing means for developing the electrostatic latent image with toner, transfer means for transferring the toner to the transfer target, fixing means for fixing the toner transferred to the transfer target, and the electrophotography The electrophotographic cartridge includes at least one selected from cleaning means for collecting the toner adhering to the photoreceptor.

The third aspect of the present invention is to form an electrostatic latent image by exposing the electrophotographic photosensitive member of the present invention, a charging means for charging the electrophotographic photosensitive member, and the charged electrophotographic photosensitive member. The image forming apparatus includes an exposure unit, a developing unit that develops the electrostatic latent image with toner, and a transfer unit that transfers the toner to a transfer target.
The fourth gist of the present invention resides in an enamine compound represented by the following general formula [I].

(In the formula [1], R is the same or different, and the substituent constant σp in Hammett's rule is 0.20 or less, represents an organic group having 1 to 6 carbon atoms, and m represents an integer of 0 to 5. Ar ¹ has a substituent constant σp in the Hammett rule of 0.20 or less and a phenyl group having at least one organic group having 1 to 6 carbon atoms, or a substituent constant σp in the Hammett rule of 0.20 or less, A condensed polycyclic hydrocarbon group which may have an organic group of 1 to 6. Ar ² has a substituent constant σp in the Hammett rule of 0.20 or less, and an organic group of 1 to 6 carbon atoms R ¹ represents an alkyl group having 1 to 4 carbon atoms and may form a ring with Ar ^2. )

  The low molecular weight enamine compound of the present invention has relatively good characteristics such as photosensitivity, residual potential, and charge mobility, and when incorporated in the photosensitive layer of an electrophotographic photosensitive member, poor cleaning, filming, dirt, afterimage. It is possible to provide an electrophotographic photosensitive member with less (ghost) and lowering of density. Also, by using this electrophotographic photosensitive member, it is possible to provide an electrophotographic cartridge and an image forming apparatus that do not generate blade reversal and rubbing noise during printing.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention. FIG. 4 is an X-ray diffraction pattern of oxytitanium phthalocyanine used in the coating liquid U for forming a charge generation layer in Examples 6 to 30 and Comparative Examples 4 to 33. FIG. 4 is an X-ray diffraction pattern of oxytitanium phthalocyanine used in the coating liquid V for forming a charge generation layer in Examples 6 to 30 and Comparative Examples 4 to 33. It is a nuclear magnetic resonance spectrum of exemplary compound CT-2 of the present invention. It is a nuclear magnetic resonance spectrum of exemplary compound CT-6 of the present invention. It is a nuclear magnetic resonance spectrum of exemplary compound CT-18 of the present invention. It is a nuclear magnetic resonance spectrum of exemplary compound CT-31 of the present invention. It is a nuclear magnetic resonance spectrum of exemplary compound CT-33 of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the present invention. it can.
<Enamine compounds>
The enamine compound of the present invention is a compound represented by the following general formula.

(In the formula [1], R is the same or different, and the substituent constant σp in Hammett's rule is 0.20 or less, represents an organic group having 1 to 6 carbon atoms, and m represents an integer of 0 to 5. Ar ¹ has a substituent constant σp in the Hammett rule of 0.20 or less and a phenyl group having at least one organic group having 1 to 6 carbon atoms, or a substituent constant σp in the Hammett rule of 0.20 or less, A condensed polycyclic hydrocarbon group which may have an organic group of 1 to 6. Ar ² has a substituent constant σp in the Hammett rule of 0.20 or less, and an organic group of 1 to 6 carbon atoms R ¹ represents an alkyl group having 1 to 4 carbon atoms and may form a ring with Ar ^2. )
In the general formula [1], R is a substituent constant σp in Hammett's rule of 0.20 or less, preferably an organic group having 1 to 6 carbon atoms, more preferably an organic group having 1 to 2 carbon atoms, It may be the same or different. For example, methyl, ethyl, n-propyl, n-butyl, isobutyl, methoxy, ethoxy and the like can be mentioned. From the viewpoint of electrical characteristics and production cost, R preferably has an organic group having 1 carbon atom.

  Here, Hammett's rule is an empirical rule used to explain the effect of a substituent in an aromatic compound on the electronic state of an aromatic ring, and the substituent constant σp of the substituted benzene is the electron donation / It can be said that this is a value obtained by quantifying the degree of suction. If the σp value is positive, the substituted benzoic acid is more acidic than the unsubstituted one, that is, an electron-withdrawing substituent. Conversely, when the σp value is negative, an electron donating substituent is formed. Table 1 shows σp values of representative substituents (The Chemical Society of Japan, “Chemical Handbook, Basic Edition II, 4th revised edition”, Maruzen Co., Ltd., published on September 30, 1993, p.364-365). .

In the general formula [1], m is 0 to 5, and an integer of 1 to 3 is preferable, but an integer of 1 to 2 is particularly preferable from the viewpoint of manufacturing cost. When m is 2 or more, Rs may be bonded to each other to form a cyclic structure.
In the general formula [1], Ar ¹ has a substituent constant σp in Hammett's rule of 0.20 or less, a phenyl group having at least one organic group having 1 to 6 carbon atoms, or substituent constant σp in Hammett's rule Is a condensed polycyclic hydrocarbon group which may have an organic group having 1 to 6 carbon atoms. For example, phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl. From the viewpoint of production cost, a condensed polycyclic hydrocarbon group having 6 to 13 carbon atoms such as phenyl, naphthyl and fluorenyl is particularly preferred. Furthermore, when having a substituent, the substituent has a substituent constant σp in the Hammett rule of 0.20 or less,
An organic group having 1 to 6 carbon atoms is preferable, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 2 to 4 carbon atoms, and the like. Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, butoxy, N, N-dimethylamino, N, N-diethylamino and the like. Among these, a substituent having 1 to 2 carbon atoms is particularly preferable from the viewpoint of electrical characteristics and production cost.

In the general formula [1], Ar ² is an aryl group having a substituent constant σp in the Hammett rule of 0.20 or less and optionally having an organic group having 1 to 6 carbon atoms. Examples include phenyl and naphthyl. From the viewpoint of production cost, a phenyl group is particularly preferable. Further, when having a substituent, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 4 carbon atoms, and the like. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, butoxy, N, N-dimethylamino, N, N-diethylamino and the like. Among them, the case where there is no substituent is particularly preferable from the viewpoint of electrical characteristics and production cost.

In the general formula [1], R ¹ is an alkyl group having 1 to 4 carbon atoms, and Ar ² may mutually form a ring. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like can be mentioned. From the viewpoint of electrical characteristics and production cost, R ¹ is particularly preferably a methyl group or a substituent capable of forming a ring structure with Ar ² .
In the enamine compound represented by the general formula [1], Ar ² and R ¹ are different from each other as described below. Therefore, a cis form (Z-form) and a trans form are present with respect to the double bond of the enamine structure. Both types (E bodies) exist at the same time. In the synthesis method of the present invention, there is no selectivity for the cis form (Z form) and the trans form (E form), and any isomer can be produced in the same ratio. Therefore, the enamine compound related to the present invention may be cis type (Z form), trans type (E form), or a mixed form of these arbitrary ratios with respect to the double bond of the enamine structure. The content ratio of the body is not limited.

  Representative examples of enamine compounds represented by the general formula [1] include the following exemplified compounds CT-1 to CT-39. However, the enamine compounds related to the present invention are not limited to these compounds.

  These enamine derivatives can be easily synthesized by combining known methods. For example, exemplary compound CT-2 of the present invention can be produced according to the following reaction formula.

The diarylamine derivative A can be condensed with the aldehyde derivative B by reflux dehydration in the presence of an acid catalyst such as acetic acid to obtain the target charge transport material CT-2.
<Electrophotographic photoreceptor>
The configuration of the electrophotographic photosensitive member of the present invention will be described below. The structure of the electrophotographic photosensitive member of the present invention is not particularly limited as long as the photosensitive layer containing the above-described enamine compound is provided on a conductive support. Among these, a laminated type photoreceptor in which a charge generation layer and a charge transport layer are laminated is preferable, and in particular, the charge transport layer preferably contains the above-described enamine compound.

(Conductive support)
There are no particular restrictions on the conductive support, but for example, metal materials such as aluminum, aluminum alloys, stainless steel, copper and nickel, and conductive powders such as metal, carbon and tin oxide can be added to make the conductive material conductive. Mainly used are resin, glass, paper, or the like obtained by depositing or coating the applied resin material or a conductive material such as aluminum, nickel, or ITO (indium tin oxide) on its surface. These may be used alone or in combination of two or more in any combination and ratio. As a form of the conductive support, a drum form, a sheet form, a belt form or the like is used. Furthermore, a conductive material having an appropriate resistance value may be used on a conductive support made of a metal material in order to control conductivity and surface properties and to cover defects.

  Moreover, when using metal materials, such as an aluminum alloy, as an electroconductive support body, you may use, after giving an anodic oxide film. When an anodized film is applied, it is desirable to perform a sealing treatment by a known method. The surface of the conductive support may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, it may be roughened by mixing particles having an appropriate particle size with the material constituting the conductive support. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process.

(Underlayer)
An undercoat layer may be provided between the conductive support and the photosensitive layer described later for improving adhesion and blocking properties. As the undercoat layer, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used.
Examples of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. One kind of these particles may be used alone, or a plurality of kinds of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicon. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Moreover, the thing of a several crystal state may be contained.

In addition, various particle sizes of metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle size is preferably 10 nm or more and 100 nm or less, and particularly 10 nm or more and 50 nm or less. preferable.
The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. The binder resin used for the undercoat layer is epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, chloride resin. Cellulose esters such as vinylidene resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacryl resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyvinyl pyridine resin, water-soluble polyester resin, nitrocellulose Resin, cellulose ether resin, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelate compound, zirconium The organic zirconium compound alkoxide compounds, titanyl chelate compounds, organic titanyl compounds such as titanium alkoxide compounds include known binder resins such as a silane coupling agent. These may be used alone or in combination of two or more in any combination and ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamides, modified polyamides, and the like are preferable because they exhibit good dispersibility and coatability.

The use ratio of the inorganic particles to the binder resin used in the undercoat layer can be arbitrarily selected, but is usually in the range of 10% by mass or more and 500% by mass or less from the viewpoint of the stability of the dispersion and the coating property. Is preferably used.
The thickness of the undercoat layer can be arbitrarily selected, but is usually preferably in the range of 0.1 μm or more and 20 μm or less from the viewpoint of improving the photoreceptor characteristics and coating properties. A known antioxidant or the like may be mixed in the undercoat layer. For the purpose of preventing image defects, pigment particles, resin particles and the like may be included.

(Photosensitive layer)
As a type of the photosensitive layer, a charge generation material and a charge transport material are present in the same layer and are dispersed in a binder resin, a charge generation layer in which a charge generation material is dispersed in a binder resin, and a charge. Examples thereof include a functional separation type (lamination type) composed of two layers of a charge transport layer in which a transport material is dispersed in a binder resin. The photosensitive layer in the invention may be of any type.

In addition, as the laminated photosensitive layer, a charge-generating layer and a charge transport layer are laminated in this order from the conductive support side, and conversely, a charge transport layer and a charge generation layer are formed from the conductive support side. There are reverse laminated photosensitive layers provided in order, and any of them can be adopted, but a forward laminated photosensitive layer that can exhibit the most balanced photoconductivity is preferable.
(Laminated photosensitive layer)
-Charge generation layer In the case of a multilayer type photoreceptor (function-separated type photoreceptor), the charge generation layer is formed by binding a charge generation substance with a binder resin.

  Examples of the charge generation material include inorganic photoconductive materials such as selenium and its alloys, cadmium sulfide, and organic photoconductive materials such as organic pigments. Organic photoconductive materials are preferred, and organic photoconductive materials are particularly preferable. Pigments are preferred. Examples of organic pigments include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium) pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments. . Among these, phthalocyanine pigments or azo pigments are particularly preferable. When organic pigments are used as the charge generating substance, usually, fine particles of these organic pigments are used in the form of a dispersion layer bound with various binder resins.

  When a metal-free phthalocyanine compound or a metal-containing phthalocyanine compound is used as the charge generation material, a highly sensitive photoreceptor can be obtained with respect to a laser beam having a relatively long wavelength, for example, a laser beam having a wavelength around 780 nm. Further, when an azo pigment such as monoazo, diazo, or trisazo is used, white light, laser light having a wavelength around 660 nm, or laser light having a relatively short wavelength (for example, a wavelength in the range of 380 nm to 500 nm). It is possible to obtain a photoreceptor having sufficient sensitivity to the laser beam).

When using a phthalocyanine pigment as a charge generation material, specifically, metal such as metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, aluminum, or oxides thereof, halides, Those having each crystal form of coordinated phthalocyanines such as hydroxides and alkoxides, and phthalocyanine dimers using oxygen atoms as bridging atoms are used. Particularly, titanyl phthalocyanines (also known as oxytitanium) such as X-type, τ-type metal-free phthalocyanine, A-type (also known as β-type), B-type (also known as α-type), and D-type (also known as Y-type), which are highly sensitive crystal types Phthalocyanine), vanadyl phthalocyanine, chloroindium phthalocyanine, hydroxyindium phthalocyanine, chlorogallium phthalocyanine such as type II, hydroxygallium phthalocyanine such as type V, μ-oxo-gallium phthalocyanine dimer such as type G and type I, type II, etc. The [mu] -oxo-aluminum phthalocyanine dimer is preferred.

  Among these phthalocyanines, A-type (also known as β-type), B-type (also known as α-type), and powder X-ray diffraction angle 2θ (± 0.2 °) are 27.1 ° or 27.3 °. D-type (Y-type) titanyl phthalocyanine, II-type chlorogallium phthalocyanine, V-type hydroxygallium phthalocyanine, hydroxygallium phthalocyanine having the strongest peak at 28.1 °, or 26. Hydroxygallium phthalocyanine having no peak at 2 °, a clear peak at 28.1 °, and a full width at half maximum W of 25.9 ° of 0.1 ° ≦ W ≦ 0.4 ° G-type μ-oxo-gallium phthalocyanine dimer and the like are particularly preferable.

  The phthalocyanine compound may be a single compound or several mixed or mixed crystal states. As the mixed state in the phthalocyanine compound or crystal state here, those obtained by mixing the respective constituent elements later may be used, or the mixed state in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, crystallization, etc. It may be the one that gave rise to. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to generate a mixed crystal state, as described in JP-A-10-48859, two types of crystals are mixed, mechanically ground and made amorphous, and then converted into a specific crystal state by solvent treatment. The method of doing is mentioned.

  When an azo pigment is used as the charge generation material, various bisazo pigments and trisazo pigments are preferably used. Examples of preferred azo pigments are shown below.

  When the organic pigments exemplified above are used as the charge generation material, one kind may be used alone, or two or more kinds of pigments may be mixed and used. In this case, it is preferable to use a combination of two or more kinds of charge generating materials having spectral sensitivity characteristics in different spectral regions of the visible region and the near red region. Among them, a disazo pigment, a trisazo pigment and a phthalocyanine pigment are preferably used in combination. More preferred.

  The binder resin used for the charge generation layer is not particularly limited. Polyarylate resin, polycarbonate resin, polyester resin, modified ether-based polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, polyacrylamide resin, polyamide resin, Polyvinyl pyridine resin, cellulose resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, casein, vinyl chloride Vinyl chloride-vinyl acetate copolymer such as vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Insulating resin such as polymer, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-alkyd resin, silicon-alkyd resin, phenol-formaldehyde resin, poly-N-vinylcarbazole, polyvinylanthracene, polyvinylperylene Organic photoconductive polymers such as Any one of these binder resins may be used alone, or two or more thereof may be mixed and used in any combination.

Specifically, the charge generation layer is prepared by dispersing a charge generation material in a solution obtained by dissolving the above-described binder resin in an organic solvent to prepare a coating solution, which is then formed on a conductive support (when an undercoat layer is provided). Is formed by coating (on the undercoat layer).
The solvent used for preparing the coating solution is not particularly limited as long as it dissolves the binder resin. For example, saturated aliphatic solvents such as pentane, hexane, octane, and nonane, and aromatics such as toluene, xylene, and anisole. Group solvents, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, chloronaphthalene, amide solvents such as dimethylformamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-butanol, benzyl alcohol, etc. Alcohol solvents, aliphatic polyhydric alcohols such as glycerin and polyethylene glycol, chain or cyclic ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, 4-methoxy-4-methyl-2-pentanone, methyl formate, ethyl acetate, Acetic acid n-bu Chains such as ester solvents such as benzene, halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, etc. Or cyclic ether solvents, acetonitrile, dimethyl sulfoxide, sulfolane, aprotic polar solvents such as hexamethylphosphoric triamide, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine-containing nitrogen Compound, mineral oil such as ligroin, water and the like. Any one of these may be used alone, or two or more of these may be used in combination. In addition, when providing the above-mentioned undercoat layer, what does not melt | dissolve this undercoat layer is preferable.

  In the charge generation layer, the compounding ratio (mass ratio) of the binder resin and the charge generation material is usually 10 parts by mass or more, preferably 30 parts by mass or more, and usually 1000 parts by mass with respect to 100 parts by mass of the binder resin. The range is not more than part by mass, preferably not more than 500 parts by mass. The film thickness of the electrification generation layer is usually in the range of 0.1 μm or more, preferably 0.15 μm or more, and usually 10 μm or less, preferably 0.6 μm or less. If the ratio of the charge generation material is too high, the stability of the coating solution may be reduced due to aggregation of the charge generation material. On the other hand, if the ratio of the charge generating substance is too low, the sensitivity as a photoreceptor may be reduced.

As a method for dispersing the charge generation material, a known dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. At this time, it is effective to refine the particles to a particle size in the range of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.
-Charge transport layer The charge transport layer of the multilayer photoconductor contains a charge transport material and usually contains a binder resin and other components used as necessary. Specifically, such a charge transport layer is prepared by dissolving or dispersing a charge transport material or the like and a binder resin in a solvent to prepare a coating solution. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (on the undercoat layer when an undercoat layer is provided).

As the charge transport material, the enamine compound of the present invention is preferably used. As the enamine compound of the present invention, one kind may be used alone, or a plurality of kinds may be combined in any ratio.
In addition to the enamine compound of the present invention, other known charge transport materials may be used in combination. When other charge transport materials are used in combination, the kind thereof is not particularly limited. For example, carbazole derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, and those obtained by bonding a plurality of these derivatives are preferable. More specifically, it is described in JP-A-2-230255, JP-A-63-225660, JP-A-58-198043, JP-B-58-32372, and JP-B-7-21646. Compounds are preferably used. Any of these charge transport materials may be used alone, or a plurality of types may be used in any combination. When the enamine compound of the present invention is used in combination with another known charge transport material, the content ratio (% by mass) of the charge transport material to be used in the total amount of the charge transport material is not particularly limited, but is 1% or more. It is preferably within a range of 20% or less, and in order to more effectively exert the role of the enamine compound of the present invention, 3% or more and 10%
The following range is particularly preferable.

  The binder resin is used for securing the film strength. Examples of the binder resin for the charge transport layer include polymers and copolymers of vinyl compounds such as butadiene resin, styrene resin, vinyl acetate resin, vinyl chloride resin, acrylic ester resin, methacrylic ester resin, vinyl alcohol resin, and ethyl vinyl ether. Polymer, polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal, polycarbonate resin, polyester resin, polyarylate resin, polyamide resin, polyurethane resin, cellulose ester resin, phenoxy resin, silicon resin, silicon-alkyd resin, poly-N -Vinyl carbazole resin etc. are mentioned. Of these, polycarbonate resins and polyarylate resins are preferred. These binder resins can also be used after being crosslinked by heat, light or the like using an appropriate curing agent. Any one of these binder resins may be used alone, or two or more thereof may be used in any combination.

  As for the ratio of the binder resin to the charge transport material, the charge transport material is used in a ratio of 20 parts by mass or more with respect to 100 parts by mass of the binder resin. In order to fully demonstrate the effects of the present invention, the amount is usually 30 parts by weight or more, preferably 40 parts by weight or more, more preferably 50 parts by weight or more, and the upper limit is preferably 100 parts by weight of the binder resin. Is 120 parts by weight or less, more preferably 100 parts by weight or less, and particularly preferably 80 parts by weight or less.

The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 45 μm or less, from the viewpoint of long life, image stability, and high resolution. Is in the range of 30 μm or less.
<Single layer type photosensitive layer>
The single-layer type photosensitive layer is formed using a binder resin in order to ensure film strength, in the same manner as the charge transport layer of the multilayer photoconductor, in addition to the charge generation material and the charge transport material. Specifically, a charge generation material, a charge transport material, and various binder resins are dissolved or dispersed in a solvent to prepare a coating solution, and on a conductive support (or an undercoat layer when an undercoat layer is provided). It can be obtained by coating and drying.

The types of the charge transport material and the binder resin and the use ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor. A charge generation material is further dispersed in a charge transport medium comprising these charge transport materials and a binder resin.
As the charge generation material, the same materials as those described for the charge generation layer of the multilayer photoreceptor can be used. However, in the case of a photosensitive layer of a single layer type photoreceptor, it is necessary to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

If the amount of the charge generating material dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity cannot be obtained, but if it is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. The total amount of the layer-type photosensitive layer is usually 0.5% by mass or more, preferably 1% by mass or more, and usually 50% by mass or less, preferably 20% by mass or less.
In addition, the usage ratio of the binder resin and the charge generation material in the single-layer type photosensitive layer is such that the charge generation material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the binder resin. It is 30 mass parts or less, Preferably it is set as the range of 10 mass parts or less.

The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.
<Other functional layers>
For the purpose of improving film-forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc., in both the photosensitive layer and each layer constituting it, both in the multilayer type photosensitive member and the single layer type photosensitive member. Known antioxidants,
You may contain additives, such as a plasticizer, a ultraviolet absorber, an electron withdrawing compound, a leveling agent, and a visible light shading agent.

Further, in both the laminated type photoreceptor and the single layer type photoreceptor, the photosensitive layer formed by the above procedure may be the uppermost layer, that is, the surface layer, but another layer may be provided on the photosensitive layer and used as the surface layer. Good.
For example, a protective layer may be provided for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like.
The protective layer is formed by containing a conductive material in a suitable binder resin, or a copolymer using a compound having charge transporting ability such as a triphenylamine skeleton described in JP-A-9-190004. Can be formed.

Examples of the conductive material used for the protective layer include aromatic amino compounds such as TPD (N, N′-diphenyl-N, N′-bis- (m-tolyl) benzidine), antimony oxide, indium oxide, tin oxide, and oxide. Metal oxides such as titanium, tin oxide-antimony oxide, aluminum oxide, and zinc oxide can be used, but are not limited thereto.
As the binder resin used for the protective layer, known resins such as polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, and siloxane resin can be used. Also, a skeleton having a charge transporting ability such as a triphenylamine skeleton as described in JP-A-9-190004 and a copolymer of the above resin can be used.

The electrical resistance of the protective layer is usually in the range of 10 ⁹ Ω · cm to 10 ¹⁴ Ω · cm. When the electric resistance is higher than the range, the residual potential is increased, resulting in an image with much fogging. On the other hand, when the electric resistance is lower than the range, the image is blurred and the resolution is reduced. Further, the protective layer must be configured so as not to substantially prevent transmission of light irradiated during image exposure.
Further, for the purpose of reducing the frictional resistance and wear on the surface of the photoconductor, and increasing the transfer efficiency of the toner from the photoconductor to the transfer belt and paper, etc., the surface layer is made of fluorine resin, silicon resin, polyethylene resin, or the like. You may contain the particle | grains which consist of these resin, and the particle | grains of an inorganic compound. Alternatively, a layer containing these resins and particles may be newly formed as a surface layer.

<Method for forming each layer>
Each layer constituting the above-described photoreceptor is formed by dip coating, spray coating, nozzle coating, bar coating, roll coating, blade coating on a conductive support obtained by dissolving or dispersing a substance to be contained in a solvent. It is formed by repeating a coating / drying step sequentially for each layer by a known method such as coating.

  There are no particular restrictions on the solvent or dispersion medium used for the preparation of the coating solution, but specific examples include alcohols such as methanol, ethanol, propanol and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, dimethoxyethane and the like. Ethers, esters such as methyl formate and ethyl acetate, acetone, methyl ethyl ketone, cyclohexanone, ketones such as 4-methoxy-4-methyl-2-pentanone, aromatic hydrocarbons such as benzene, toluene, xylene, dichloromethane, Chlorinated hydrocarbons such as chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, Diethyl Minh, triethanolamine, ethylenediamine, nitrogen-containing compounds such as triethylenediamine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and kinds.

The amount of the solvent or the dispersion medium used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, it is appropriately determined so that the physical properties such as the solid content concentration and viscosity of the coating liquid are within a desired range. It is preferable to adjust.
For example, in the case of a charge transport layer of a single layer type photoreceptor or a function separation type photoreceptor, the solid content concentration of the coating solution is usually 5% by mass or more, preferably 10% by mass or more, and usually 40% by mass or less. The range is preferably 35% by mass or less. In addition, the viscosity of the coating solution is usually 10 mPa · s or higher, preferably 50 mPa · s or higher, and usually 500 mPa · s or lower, preferably 400 mPa · s or lower, at the temperature during use.

  In the case of a charge generation layer of a multilayer photoreceptor, the solid content concentration of the coating solution is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass. % Or less. In addition, the viscosity of the coating solution is usually 0.01 mPa · s or higher, preferably 0.1 mPa · s or higher, and usually 20 mPa · s or lower, preferably 10 mPa · s or lower, at the temperature during use.

Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used.
The coating solution is preferably dried by touching at room temperature, followed by heating or drying in a temperature range of usually 30 ° C. or more and 200 ° C. or less for 1 minute to 2 hours, while still or blowing. Further, the heating temperature may be constant, or heating may be performed while changing the temperature during drying.

<Image forming apparatus and electrophotographic cartridge>
Next, an embodiment of an image forming apparatus (hereinafter referred to as “image forming apparatus of the present invention” as appropriate) using the electrophotographic photoreceptor of the present invention (hereinafter referred to as “photosensitive body” as appropriate) will be described. A description will be given with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily changed and implemented without departing from the gist of the present invention.

As shown in FIG. 2, the image forming apparatus includes a photoreceptor 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6, and a fixing device 7 as necessary. Is provided.
The photoreceptor 1 is not particularly limited as long as it is the above-described photoreceptor of the present invention. In FIG. 2, as an example, a drum-shaped photoreceptor in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. Is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are arranged along the outer peripheral surface of the photoreceptor 1.

  The charging device 2 charges the photoreceptor 1 and uniformly charges the surface of the photoreceptor 1 to a predetermined potential. Examples of the charging device include a corona charging device such as corotron and scorotron, a direct charging device (contact type charging device) for charging a direct charging member to which a voltage is applied by contacting the photosensitive member surface, and a contact type charging device such as a charging brush. Often used. Examples of the direct charging means include a contact charger such as a charging roller and a charging brush. In FIG. 2, a roller-type charging device (charging roller) is shown as an example of the charging device 2. As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Moreover, as a voltage applied at the time of charging, it is possible to use only a direct current voltage or to superimpose an alternating current on a direct current.

The type of the exposure device 3 is not particularly limited as long as it can expose the photosensitive member 1 to form an electrostatic latent image on the photosensitive surface of the photosensitive member 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a wavelength shorter than 380 nm to 500 nm. . Among these, it is preferable to use light having a short wavelength of 380 to 500 nm because the resolution becomes high. Among these, 405 nm monochromatic light is preferable. Also, the writing resolution is currently 600dp
Although i is the mainstream, there are some 1200 dpi high-performance models. The resolution of the electrostatic latent image and the toner image is determined depending on the writing resolution, and the higher the resolution, the clearer the image is obtained. Therefore, a resolution of 1200 dpi or higher is preferable. For example, when writing is performed with an LED having a resolution of 600 dpi and 1200 dpi, the minimum dot formation interval is 42 μm and 21 μm, respectively.

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 2, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which the toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. This replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge. In this embodiment, the toner T is preferably a toner having an average circularity measured by a flow particle image analyzer of 0.960 or more and 1.000 or less.

The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicone resin, a urethane resin, a fluororesin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.
The developing roller 44 is disposed between the photoreceptor 1 and the supply roller 43, and is in contact with the photoreceptor 1 and the supply roller 43. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the photoreceptor 1.

  The regulating member 45 is formed of a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with a resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.
The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like disposed so as to face the photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the photoreceptor 1 onto a recording paper (paper, medium) P. is there.

There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner. If there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.

  Among these, a blade cleaning system having a blade cleaning mechanism is preferable because of its simple structure, small size, low cost, and excellent cleaning performance and reliability. The blade cleaning method can be classified into a contact method and a pressurization method (57th Annual Meeting of the Imaging Society of Japan P196-211). The contact method is classified into counter contact and forward contact, and the pressurization method is classified into a low displacement method and a low load method.

In the present invention, a blade cleaning method is preferable for effectively removing the toner. In particular, when a toner having a high degree of circularity is used, the toner easily slips between the blade and the photosensitive member. Is preferred. The linear pressure of the blade against the photoreceptor is preferably 20 g / cm or more, and preferably 60 g / cm or less.
If the blade is set under the above conditions, rubbing noise may occur between the photoconductor and the blade, but this can be avoided by using the photoconductor of the present invention.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 2 shows an example in which a heating device 73 is provided inside the upper fixing member 71. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube made of stainless steel, aluminum or the like is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, a fixing sheet, or the like. A member can be used. Further, the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve the releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
The type of the fixing device is not particularly limited, and a fixing device of an arbitrary method such as heat roller fixing, flash fixing, oven fixing, pressure fixing, or the like can be provided.

In the image forming apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.
Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.
When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. The toner image is transferred to the transfer device 5.
Is transferred onto the recording paper P. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6. At this time, by using the above-described cleaning device, when the electrophotographic photosensitive member of the present invention is used as the photosensitive member 1, advantages such as suppression of the occurrence of cleaning failure and more efficient recovery of the toner T can be obtained. .

After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.
In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The charge eliminating step is a step of discharging the photosensitive member by exposing the photosensitive member, and a fluorescent lamp, LED, or the like is used as the discharging device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of exposure light.

In addition, the image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.
The electrophotographic photosensitive member 1 is combined with one or more of the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7 to form an integrated cartridge ( The electrophotographic photosensitive member cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. In this case, for example, when the electrophotographic photosensitive member 1 and other members are deteriorated, the electrophotographic photosensitive member cartridge is removed from the main body of the image forming apparatus, and another new electrophotographic photosensitive member cartridge is mounted on the main body of the image forming apparatus. This facilitates maintenance and management of the image forming apparatus.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples, production examples, examples and comparative examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.
<Manufacture of enamine compounds>
(Synthesis Example 1: Production of Exemplified Compound CT-2)
In a nitrogen atmosphere, a reflux tube and a Dean-stark water separator were set in the reactor in order, and N, N-di (3,4-
Xylyl) amine 6.76 g (30 mmol), 2-phenylpropionaldehyde (racemic) 4.43
g (33 mmol), 30 ml of acetic acid, and 30 ml of toluene were charged into the reactor, and the mixture was stirred for 2 hours under reflux and cooled to room temperature. The reaction solution and toluene / demineralized water (v / v = 1: 1) were mixed and stirred and separated. The obtained organic layer was washed with 1 N NaOH aqueous solution and separated, and the organic layer was further washed with demineralized water 2-3 times and separated. The solvent of the obtained organic layer was distilled off under reduced pressure, passed through flash column chromatography [45 μm activated alumina (manufactured by Sumitomo Chemical Co., Ltd.) 400 g, developing solvent: toluene / hexane = 1/3], and further reprecipitated with methanol. Purified. After vacuum drying, the exemplified compound CT-2 was obtained as white crystals (yield 8.91 g, yield 84%, purity 99.5%). The purity was calculated from the simple area ratio value on the high performance liquid chromatography chart. A nuclear magnetic resonance spectrum (300 MHz, Varian Gemini-2000 NMR spectrometer) of this compound is shown in FIG.

(Synthesis Example 2: Production of Exemplified Compound CT-18)
Exemplified compound CT-18 was obtained as a pale yellow powder in the same manner as in Synthesis Example 1, except that N- (6-methoxy-2-naphthyl) -N- (p-tolyl) amine was used as a raw material. The nuclear magnetic resonance spectrum (300 MHz, Varian Gemini-2000 NMR spectrometer) of this compound is shown in FIG.
(Synthesis Example 3: Production of Exemplified Compound CT-6)
Exemplified compound CT-6 was obtained as white crystals in the same manner as in Synthesis Example 1, except that N, N'-di (p-tolyl) amine and an aldehyde (racemic) having the following structure were used as raw materials. . The nuclear magnetic resonance spectrum (300 MHz, Varian Gemini-2000 NMR spectrometer) of this compound is shown in FIG.

(Synthesis Example 4: Production of Exemplified Compound CT-31)
The same procedure as in Synthesis Example 1 except that N- (6-methoxy-2-naphthyl) -N- (p-methoxyphenyl) amine and the aldehyde (racemic) used in Production Example 3 were used as raw materials. Thus, Exemplified Compound CT-31 was obtained as a light yellow powder. The nuclear magnetic resonance spectrum (300 MHz, Varian Gemini-2000 NMR spectrometer) of this compound is shown in FIG.

(Synthesis Example 5: Production of Exemplified Compound CT-33)
Similar to Synthesis Example 1 except that N- (6-methoxy-2-naphthyl) -N- (3,4-xylyl) amine and the aldehyde (racemic) used in Production Example 3 were used as raw materials. By operation, Exemplified Compound CT-33 was obtained as a light yellow powder. The nuclear magnetic resonance spectrum (300 MHz, Varian Gemini-2000 NMR spectrometer) of this compound is shown in FIG.

(Example 1: Electrophotographic photoreceptor A1)
Using a conductive support in which an aluminum vapor-deposited layer (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), the following undercoat layer dispersion is formed on the aluminum vapor-deposited layer of the conductive support The liquid was applied by a bar coater so that the film thickness after drying was 1.25 μm and dried to form an undercoat layer.

The undercoat layer dispersion was prepared by the following method. That is, a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by mass of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide were flowed at high speed. Disperse the surface-treated titanium oxide obtained by mixing at high speed with a rotary mixing speed of 34.5 m / sec using a ball mill of methanol / 1-propanol. Thus, a dispersion slurry of hydrophobized titanium oxide was obtained. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (C)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula ( Compound represented by D)] / hexamethylenediamine [compound represented by the following formula (E)] / decamethylene dicarboxylic acid [compound represented by the following formula (F)] / octadecamethylene dicarboxylic acid [following formula The compositional molar ratio of the compound represented by (G) is 60%
/ 15% / 5% / 15% / 5% of the copolymerized polyamide pellets are heated and stirred and mixed to dissolve the polyamide pellets, and then subjected to ultrasonic dispersion treatment to obtain methanol / 1- An undercoat layer dispersion having a solid content concentration of 18.0% and containing a propanol / toluene mass ratio of 7/1/2 and a hydrophobically-treated titanium oxide / copolymerized polyamide at a mass ratio of 3/1.

  Next, 10 parts of oxytitanium phthalocyanine having a powder X-ray diffraction spectrum shown in FIG. In addition to 150 parts of 2-dimethoxyethane, pulverization and dispersion treatment was performed with a sand grind mill to prepare a pigment dispersion. 160 parts of the pigment dispersion thus obtained, 100 parts of a 5% 1,2-dimethoxyethane solution of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name # 6000C), an appropriate amount of 1,2-dimethoxyethane, Were finally mixed to prepare a dispersion having a solid content of 4.0%.

The dispersion was applied on the undercoat layer with a wire bar so that the film thickness after drying was 0.4 μm, and then dried to form a charge generation layer.
Next, 50 parts of a charge transport material of enamine compound CT-2, 100 parts of the following polycarbonate resin (5), 0.05 part of silicone oil as a leveling agent, a mixed solvent of tetrahydrofuran and toluene (tetrahydrofuran 80% by weight, toluene 20% by weight) %) Was mixed with 640 parts to prepare a coating solution for forming a charge transport layer. This liquid is applied onto the above-described charge generation layer using an applicator so that the film thickness after drying is 25 μm, and dried at 125 ° C. for 20 minutes to form a charge transport layer, whereby the photosensitive sheet A1 is obtained. Produced. The viscosity average molecular weight of the polycarbonate resin (H) was 30,000.

The measuring method of the viscosity average molecular weight of the used binder resin is as follows. Dissolve the resin in dichloromethane to prepare a solution with a concentration C of 6.00 g / L. The flow time t of the sample solution is measured in a constant temperature water bath set to 20.0 ° C. using an Ubbelohde capillary viscometer with a flow time t ₀ of the solvent (dichloromethane) of 136.16 seconds. The viscosity average molecular weight Mv is calculated according to the following formula.

a = 0.438 × η _sp +1 η _sp = t / t ₀ −1
b = 100 × η _sp / C C = 6.00 (g / L)
η = b / a
Mv = 3207 × η ^1.205
(Example 2: electrophotographic photoreceptor A2)
An electrophotographic photoreceptor A2 as an example was obtained in the same manner as in Example 1 except that CT-18 was used as the charge transport material instead of the exemplified compound CT-2.

(Example 3: electrophotographic photoreceptor A3)
An electrophotographic photoreceptor A3 as an example was obtained in the same manner as in Example 1 except that CT-6 was used as a charge transport material instead of the exemplified compound CT-2.
(Example 4: electrophotographic photoreceptor A4)
An electrophotographic photoreceptor A4 as an example was obtained in the same manner as in Example 1 except that CT-31 was used as the charge transport material instead of the exemplified compound CT-2.

(Example 5: electrophotographic photoreceptor A5)
An electrophotographic photoreceptor A5 as an example was obtained in the same manner as in Example 1 except that CT-33 was used as a charge transport material instead of the exemplified compound CT-2.
(Comparative Example 1: Electrophotographic photoreceptor P1)
An electrophotographic photoreceptor P1 as a comparative example was obtained in the same manner as in Example 1 except that the following charge transport material (J) was used instead of the exemplified compound CT-2.

(Comparative Example 2: Electrophotographic photoreceptor P2)
An electrophotographic photoreceptor P2 as a comparative example was obtained in the same manner as in Example 1 except that the following charge transport material (K) was used instead of the exemplified compound CT-2.

(Comparative Example 3: Electrophotographic photoreceptor P3)
An electrophotographic photoreceptor P3 as a comparative example was obtained in the same manner as in Example 1 except that the following charge transport material (L) was used instead of the exemplified compound CT-2.

[Characteristic evaluation]
The manufactured electrophotographic photoreceptors A1 to A5 and P1 to P3 were subjected to the following electrical property tests.
<Electrical characteristics test>
An electrophotographic characteristic evaluation apparatus manufactured according to the electrophotographic society measurement standard (basic and applied electrophotographic technology, edited by the Electrophotographic Society, Corona, pages 404 to 405) is used, and the photoreceptor sheet has an outer diameter of 80 mm. After the aluminum drum and the aluminum substrate of the photosensitive sheet are connected to each other, the drum is rotated at a constant rotational speed of 60 rpm to charge, expose, measure potential, and remove static electricity. An electrical property evaluation test by cycle was performed. At that time, the photosensitive member was charged so that the initial surface potential was − (minus, the same applies hereinafter) to 700 V, and the light from the halogen lamp was converted to monochromatic light of 780 nm with an interference filter and exposed at 1.0 μJ / cm ² . The post-exposure surface potential after 100 milliseconds (hereinafter sometimes referred to as Vl) was measured. In measuring Vl, the time required from the exposure to the potential measurement was set to 100 ms, which was a fast response condition. Further, the photoreceptor surface potential is -700 V to -350.
The half exposure energy E1 / 2 (μJ / cm2) required to reach V was determined. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50%.

  Table 2 shows the evaluation results of the electrophotographic photoreceptors A1 to A5 and P1 to P2.

As shown in Table 2, the photoreceptor using the enamine charge transport material of the present invention represented by the general formula [1] exhibits superior electrical characteristics as compared to the enamine charge transport materials J, K, and L. I understand that.
(Production Example 1)
100 parts of a polyarylate resin having the following repeating structure (resin 1, viscosity average molecular weight 43000), 80 parts of CT-2 as a charge transport material, and 0.05 parts of silicone oil as a leveling agent, THF / toluene (8 / 2 (weight ratio)) was dissolved in 640 parts of a mixed solvent to prepare a coating solution for forming a charge transport layer.

(Production Example 2)
A coating solution for forming a charge transport layer was prepared in the same manner as in Production Example 1, except that CT-18 was used as the charge transport material instead of CT-2 used in the coating solution for forming a charge transport layer in Production Example 1. did.
(Production Example 3)
A coating solution for forming a charge transport layer was prepared in the same manner as in Production Example 1, except that CT-6 was used as the charge transport material instead of CT-2 used in the coating solution for forming a charge transport layer in Production Example 1. did.

(Production Example 4)
A coating solution for forming a charge transport layer was prepared in the same manner as in Production Example 1 except that CT-31 was used as the charge transport material instead of CT-2 used in the coating solution for forming the charge transport layer in Production Example 1. did.
(Production Example 5)
A coating solution for forming a charge transport layer was prepared in the same manner as in Production Example 1, except that CT-33 was used as the charge transport material instead of CT-2 used in the coating solution for forming the charge transport layer in Production Example 1. did.

(Production Examples 6-10)
Manufacture except that the polyarylate resin (resin 2, viscosity average molecular weight 43200) having the following repeating structure was used instead of the polyarylate resin (resin 1) used in the charge transport layer forming coating solution of Production Example 1. In the same manner as in Examples 1 to 5, coating liquids for forming a charge transport layer were prepared as Production Examples 6 to 10, respectively.

(Production Examples 11-15)
Manufacture except that the polyarylate resin (resin 3, viscosity average molecular weight 44000) having the following repeating structure was used in place of the polyarylate resin (resin 1) used in the coating liquid for forming the charge transport layer in Production Example 1. In the same manner as in Examples 1 to 5, coating liquids for forming a charge transport layer were prepared as Production Examples 11 to 15, respectively.

(Production Examples 16-20)
50 parts by weight of the polyarylate resin (resin 1) used in the coating liquid for forming the charge transport layer of Production Example 1 and 50 parts by weight of a polycarbonate resin (resin 4, viscosity average molecular weight 50000) having the following repeating structure: Except for using, in the same manner as in Production Examples 1 to 5, as Production Examples 16 to 20, coating liquids for forming a charge transport layer were prepared.

(Production Examples 21-25)
Except for using the polycarbonate resin 5 used in Example 1 instead of the polyarylate resin (resin 1) used in the coating liquid for forming the charge transport layer of Production Example 1, the same as Production Examples 1 to 5, As Production Examples 21 to 25, coating liquids for forming a charge transport layer were prepared.
(Comparative Production Examples 1-5)
Instead of the enamine compound of the present invention used in the coating liquid for forming a charge transport layer in Production Examples 1 to 25,
Using the following enamine charge transport material M exemplified in Patent Document 1, and further using the resins used in Production Examples 1, 6, 11, 16, and 21, in the same order, a coating solution for forming a charge transport layer Were prepared respectively.

(Comparative Production Examples 6 to 10)
Instead of the enamine compound of the present invention used in the coating liquid for forming a charge transport layer in Production Examples 1 to 25,
Using the following enamine charge transport material N exemplified in Patent Document 1, and further using the resins used in Production Examples 1, 6, 11, 16, and 21, in the same order, a coating solution for forming a charge transport layer Were prepared respectively.

(Comparative Production Examples 11-15)
Instead of the enamine compound of the present invention used in the coating liquid for forming a charge transport layer in Production Examples 1 to 25,
Using the following enamine charge transport material Q exemplified in Patent Document 2, and further using the resins used in Production Examples 1, 6, 11, 16, and 21, in the same order, a coating solution for forming a charge transport layer Were prepared respectively.

(Comparative Production Examples 16-20)
Instead of the enamine compound of the present invention used in the coating liquid for forming a charge transport layer in Production Examples 1 to 25,
Using the enamine charge transport material R described below, and further using the resins used in Production Examples 1, 6, 11, 16, and 21, the charge transport layer forming coating solution was prepared in the same order. Since the compatibility with the resin was poor, it could not be dissolved and a cloudy liquid was obtained and could not be used.

(Comparative Production Examples 21-25)
Instead of the enamine compound of the present invention used in the coating liquid for forming a charge transport layer in Production Examples 1 to 25,
A coating solution for forming a charge transport layer was prepared in the same order using the enamine charge transport material S described below and further using the resins used in Production Examples 1, 6, 11, 16, and 21.

(Comparative Production Examples 26-30)
Instead of the enamine compound of the present invention used in the coating liquid for forming a charge transport layer in Production Examples 1 to 25,
Using the enamine charge transport material T described below, and further using the resins used in Production Examples 1, 6, 11, 16, and 21, coating solutions for forming a charge transport layer were prepared in the same order.

(Examples 6-30, Comparative Examples 4-33)
The coating solution for forming the undercoat layer described in Example 1 and the following coating for forming the charge generation layer are formed on an aluminum cylinder having a mirror-finished outer diameter of 30 mm, a length of 260.5 mm, and a wall thickness of 0.75 mm. The coating solution for forming a charge transport layer obtained in each of the above production examples or comparative production examples is sequentially applied by a dip coating method so that the film thickness after drying becomes 1.3 μm, 0.4 μm, and 25 μm, respectively. Then, an undercoat layer, a charge generation layer, and a charge transport layer were formed to obtain photosensitive drums A6 to A30 and P4 to P33.

  The charge generation layer forming coating solution was prepared as follows. As a charge generation material, 20 parts of oxytitanium phthalocyanine and 280 parts of 1,2-dimethoxyethane showing the X-ray diffraction spectrum by CuKα characteristic X-ray in FIG. 2 are mixed, and pulverized and dispersed in a sand grind mill for 1 hour. Processing was performed. Subsequently, 10 parts of polyvinyl butyral (trade name “Denka Butyral” # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) was added to 255 parts of 1,2-dimethoxyethane and 4-methoxy-4-methyl. A binder solution obtained by dissolving in a mixed solution of 85 parts of -2-pentanone and 230 parts of 1,2-dimethoxyethane were mixed to prepare a coating solution U for forming a charge generation layer.

As a charge generation material, 20 parts of oxytitanium phthalocyanine showing X-ray diffraction spectrum by CuKα characteristic X-ray in FIG. 3 and 280 parts of 1,2-dimethoxyethane are mixed and pulverized in a sand grind mill for 4 hours to be atomized and dispersed. Processing was performed. Subsequently, 10 parts of polyvinyl butyral (trade name “Denka Butyral” # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) was added to 255 parts of 1,2-dimethoxyethane and 4-methoxy-4-methyl. A binder liquid obtained by dissolving in 85 parts of 2-pentanone and 230 parts of 1,2-dimethoxyethane were mixed to prepare a coating solution V for forming a charge generation layer.

The charge generation layer forming coating solution U and the charge generation layer forming coating solution V are mixed at a weight ratio of 8: 2 to prepare the charge generation layer forming coating solution used in Examples 6 to 30 and Comparative Examples 4 to 33. did.
Here, an image characteristic test was performed using the produced photosensitive drum and toner W having an average circularity of 0.990.
The image characteristic test was performed using a color printer HP Color LaserJet 4700dn (cleaning blade, counter contact method) manufactured by Hewlett-Packard Company.

The produced photosensitive drum and toner were mounted on a cyan process cartridge, and this cartridge was mounted on a printer. 10,000 images were formed under an environment of a temperature of 25 ° C. and a humidity of 50%, and ghosts, fogging, density reduction, filming, and poor cleaning were evaluated.
In the image forming apparatus using the electrophotographic photosensitive member of Examples 6 to 30, before image formation and 10
Even after the 000-sheet image formation, a good image with no image deterioration such as ghost, fogging, density reduction, filming, and poor cleaning was obtained. In addition, no abnormal noise was generated during printing.

In the image forming apparatuses using the electrophotographic photosensitive members of Comparative Examples 4 to 33, various types of image deterioration or abnormal noise during printing occurred.
The results are summarized in Table 3 together with the enamine charge transport material and the binder resin.

As can be seen from the comparison between Examples 6 to 30 and Comparative Examples 4 to 33 in Table 3, in the image forming apparatus using the electrophotographic photosensitive member containing the enamine charge transport material of the present invention, before image formation and 1
Even after the 0000-sheet image formation, a good image with no image deterioration such as ghost, fog, density reduction, filming, and poor cleaning was obtained. In addition, no abnormal noise was generated during printing. On the other hand, in an image forming apparatus using an electrophotographic photosensitive member containing a known enamine charge transport material, it was confirmed that various kinds of image deterioration or abnormal noise during printing occurred.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. The electrophotographic photosensitive member and the image forming apparatus accompanying such changes are also within the technical scope of the present invention, and can be appropriately changed without departing from the spirit or concept of the invention that can be read from the claims and the entire specification. Must be understood as encompassed by.

  The present invention can be carried out in any field that requires an electrophotographic photoreceptor, and is suitable for use in, for example, a copying machine, a printer, a printing machine, and the like.

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
DESCRIPTION OF SYMBOLS 5 Transfer apparatus 6 Cleaning apparatus 7 Fixing apparatus 41 Developing tank 42 Agitator 43 Supply roller 44 Developing roller 45 Control member 71 Upper fixing member (fixing roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper (paper, medium)

Claims (3)

An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains at least one enamine compound represented by the general formula [I]. .

(In the formula [1], R is the same or different, and the substituent constant σp in Hammett's rule is 0.20 or less and represents an organic group having 1 to 2 carbon atoms, and m represents an integer of 0 to 5. Ar ¹ has a substituent constant σp in the Hammett rule of 0.20 or less, a phenyl group having at least one organic group having 1 to 2 carbon atoms, or a substituent constant σp in the Hammett rule of 0.20 or less, .Ar ² indicating the number 1-2 of which may have an organic group condensed polycyclic hydrocarbon group, a is substituent constant σp of 0.20 or less in Hammett rule, organic group having 1 to 6 carbon atoms R ¹ represents an alkyl group having 1 to 4 carbon atoms and may form a ring with Ar ^2. )   The electrophotographic photosensitive member according to claim 1, charging means for charging the electrophotographic photosensitive member, image exposure means for performing image exposure on the charged electrophotographic photosensitive member to form an electrostatic latent image, and the electrostatic Developing means for developing a latent image with toner, transfer means for transferring the toner to a transfer target, fixing means for fixing the toner transferred to the transfer target, and the toner attached to the electrophotographic photosensitive member An electrophotographic cartridge provided with at least one selected from cleaning means for recovering. The electrophotographic photosensitive member according to claim 1, charging means for charging the electrophotographic photosensitive member, exposure means for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and the electrostatic characterized in that it comprises a developing means for developing the latent image with toner, and transfer means for transferring the toner to a transfer object, an image forming equipment.

Images