JP6746437B2 - Electrophotographic photoreceptor, process cartridge, electrophotographic apparatus, and method for manufacturing electrophotographic photoreceptor - Google Patents

Description

The present invention relates to an electrophotographic photoconductor, a process cartridge having the electrophotographic photoconductor, an electrophotographic apparatus, and a method for manufacturing the electrophotographic photoconductor.

In recent years, as an electrophotographic photoreceptor (organic electrophotographic photoreceptor), one having a support, an undercoat layer on the support, and a photosensitive layer on the undercoat layer has been widely used.
It is often practiced that the undercoat layer contains metal oxide particles and an organic compound for the purpose of stabilizing electrical characteristics and suppressing image defects.

Patent Document 1 discloses a technique in which an undercoat layer contains metal oxide particles and an acceptor compound such as an anthraquinone compound.
It is particularly preferable that the acceptor compound has a group capable of reacting with the metal oxide particles. It is described that image defects such as a ghost phenomenon and fog are suppressed by containing an acceptor compound in the undercoat layer and imparting an acceptor property to the undercoat layer.
Patent Document 2 discloses a technique for suppressing the ghost phenomenon by incorporating metal oxide particles and a benzophenone compound having a hydroxy group or an amino group in the undercoat layer. The organic compound having such a substituent interacts with the metal oxide particles to facilitate the transfer of electrons between the metal oxide particles in the undercoat layer or from the photosensitive layer to the undercoat layer. Guessed.

JP 2006-221094A JP, 2013-137518, A

However, when the electrophotographic photosensitive member having the undercoat layer containing the metal oxide particles is placed in a high temperature and high humidity environment and absorbs moisture, the electric characteristics may deteriorate when it is repeatedly used. Although the configuration of the above-mentioned prior art is expected to enhance the effect of electron transfer of the metal oxide particles, even in various environments for further speeding up and image quality improvement of the electrophotographic apparatus in the future. There is a demand for an electrophotographic photosensitive member having more stable electric characteristics.

An object of the present invention is to provide an electrophotographic photosensitive member in which deterioration of electrical characteristics is suppressed when repeatedly used even when left for a while in a high temperature and high humidity environment, a process cartridge having the electrophotographic photosensitive member, and An object is to provide an electrophotographic apparatus. Another object of the present invention is to provide a method for producing the electrophotographic photosensitive member.

（式（１）中、Ｒ^１〜Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１以上６以下のアルキル基、炭素数１以上８以下のアルコキシ基、または、アミノ基を示す。Ｒ^６〜Ｒ^１０は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１以上６以下のアルキル基、炭素数１以上８以下のアルコキシ基、または、アミノ基を示す。ただし、Ｒ^６〜Ｒ^１０のうちの１つまたは２つはヒドロキシ基であり、Ｒ^６〜Ｒ^１０のうちの３つ以上がヒドロキシ基であることはない。）
（γ）下記式（２）で示される化合物

（式（２）中、Ｒ^１〜Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１以上６以下のアルキル基、炭素数１以上８以下のアルコキシ基、または、アミノ基を示す。Ａ^１は、炭素数２以上４以下のアルケニル基を示す。）
を含有することを特徴とする電子写真感光体である。 The present invention provides an electrophotographic photoreceptor having a support, an undercoat layer on the support, and a photosensitive layer on the undercoat layer,
The undercoat layer is
(Α) metal oxide particles,
(Β) a compound represented by the following formula (1), and

(In the formula (1), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. One or two of R ^{6 to} R ¹⁰ are hydroxy groups, and three or more of R ^{6 to} R ¹⁰ are not hydroxy groups.)
(Γ) Compound represented by the following formula (2)

(In the formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. . A ¹ represents an alkenyl group having 2 to 4 carbon atoms.)
It is an electrophotographic photosensitive member characterized by containing.

Further, the present invention integrally supports the electrophotographic photosensitive member and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit and a cleaning unit, and attaches to and detaches from the main body of the electrophotographic apparatus. It is a free process cartridge.

Further, the present invention is an electrophotographic apparatus including the electrophotographic photosensitive member, and a charging unit, an exposing unit, a developing unit and a transferring unit.

Further, the present invention is a method for producing an electrophotographic photoreceptor, which comprises a step of forming an undercoat layer on a support, and a step of forming a photosensitive layer on the undercoat layer,
The step of forming the undercoat layer,
(Α) metal oxide particles,
(Β) a compound represented by the above formula (1), and
(Γ) A coating liquid for an undercoat layer containing the compound represented by the above formula (2) is applied onto the support to form a coating film, and the coating film is dried and/or cured to form a coating film. It is a method for manufacturing an electrophotographic photosensitive member, which is a step of forming a pulling layer.

According to the present invention, an electrophotographic photosensitive member in which deterioration of electrical characteristics when repeatedly used even after being left for a while in a high temperature and high humidity environment is suppressed, a process cartridge having the electrophotographic photosensitive member, and An electrophotographic device can be provided. Further, according to the present invention, a method for manufacturing the electrophotographic photosensitive member can be provided.

In the electrophotographic photoreceptor of the present invention, the undercoat layer contains the following (α), (β) and (γ).

(Α) is metal oxide particles.
Examples of the metal oxide particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide, zirconium oxide, and aluminum oxide.
From the viewpoint of dispersibility in the coating liquid for the undercoat layer and the electrical characteristics of the electrophotographic photoreceptor, the metal oxide particles are preferably particles having a number average particle diameter of primary particles of 0.1 μm or less.
Further, the metal oxide particles are preferably surface-treated. Among the surface-treated metal oxide particles, surface-treated zinc oxide particles are preferable from the viewpoint of electrical characteristics of the electrophotographic photoreceptor.
In the present invention, as the metal oxide particles (α), only one kind may be used, or different kinds of metal oxides, existence or non-existence or kind of surface treatment, and specific surface area Two or more kinds such as different ones can be used in combination.

上記式（１）中、Ｒ^１〜Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１以上６以下のアルキル基、炭素数１以上８以下のアルコキシ基、または、アミノ基を示す。Ｒ^６〜Ｒ^１０は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１以上６以下のアルキル基、炭素数１以上８以下のアルコキシ基、または、アミノ基を示す。ただし、Ｒ^６〜Ｒ^１０のうちの１つまたは２つはヒドロキシ基であり、Ｒ^６〜Ｒ^１０のうちの３つ以上がヒドロキシ基であることはない。 (Β) is a compound represented by the following formula (1).

In the above formula (1), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. .. R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. ^However, a one or two hydroxy groups of R 6 ^{to R 10,} is not more than three of R 6 ^{to R 10} is a hydroxy group.

By containing the compound represented by the above formula (1) in the undercoat layer together with the metal oxide particles, the electrical characteristics of the electrophotographic photosensitive member are stabilized and an image with few image defects can be output.

Specific examples of the compound represented by the above formula (1) are shown below, but the present invention is not limited thereto.

Among these, a compound represented by the above formula (1-1), in which two adjacent R ^{6 to} R ^{10 in} the above formula (1) are hydroxy groups, and a compound represented by the above formula (1-2). Compounds are preferred from the standpoint of interaction with the metal oxide particles.

The content of the compound represented by the above formula (1) in the coating liquid for the undercoat layer is 0.1% by mass or more and 4.0% by mass or less based on the metal oxide particles in the coating liquid for the undercoat layer. Preferably. When the content of the compound represented by the above formula (1) is 0.1% by mass or more, the interaction with the metal oxide particles is further enhanced. When the content of the compound represented by the above formula (1) is 4.0% by mass or less, the stability of the undercoat layer coating liquid is less likely to decrease.

上記式（２）中、Ｒ^１〜Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１以上６以下のアルキル基、炭素数１以上８以下のアルコキシ基、または、アミノ基を示す。Ａ^１は、炭素数２以上４以下のアルケニル基を示す。 (Γ) is a compound represented by the following formula (2).

In the above formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. .. A ¹ represents an alkenyl group having 2 to 4 carbon atoms.

By incorporating the compound represented by the above formula (2) of (γ) into the undercoat layer together with the metal oxide particles represented by (α) and the compound represented by the above formula (1) of (β), an electrophotographic photoreceptor The electric characteristics of the electrophotographic photosensitive member are stabilized even when the electrophotographic photosensitive member absorbs moisture under a high temperature and high humidity environment. Regarding the reason for this effect, the present inventors presume that the compound of (γ) represented by the above formula (2) enhances the coordination of (β) to the metal oxide particles. For example, when the compound represented by the above formula (2) captures a substance which inhibits the coordination of the compound represented by the above formula (1) to the metal oxide particles, the compound represented by the above formula (1) is obtained. It becomes easy to coordinate with the metal oxide particles. As a result, it is speculated that the electrical characteristics of the electrophotographic photosensitive member may be stabilized even when the electrophotographic photosensitive member absorbs moisture.

Specific examples of the compound represented by the formula (2) are shown below, but the invention is not limited thereto.

Among these, the compound represented by the above formula (2-1) in which A ¹ in the above formula (2) is a 1-propenyl group is preferable.

The content of the compound represented by the above formula (2) in the undercoat layer coating liquid is 1.0% by mass or more and 15% by mass based on the compound represented by the above formula (1) in the undercoat layer coating liquid. % Or less is preferable. When the content of the compound represented by the formula (2) is 1.0% by mass or more, the above effects can be sufficiently obtained. When the content of the compound represented by the above formula (2) is 15% by mass or less, the stability of the undercoat layer coating liquid is less likely to decrease.

It can be confirmed by headspace gas chromatography/mass spectrometry that the undercoat layer contains the compound represented by the above formula (2).

The undercoat layer coating liquid preferably contains the binder resin (organic resin) for the undercoat layer in an amount of 10% by mass or more and 50% by mass or less based on the metal oxide particles.
As the binder resin for the undercoat layer, for example, acrylic resin, allyl resin, alkyd resin, ethyl cellulose resin, ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, phenol resin, butyral resin, poly Examples thereof include acrylate, polyacetal, polyamideimide, polyamide, polyallyl ether, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, polyvinyl alcohol, polybutadiene and polypropylene. Of these, polyurethane is preferred.
These resins may be used alone or as a mixture or a copolymer, and one kind or two or more kinds may be used.

The undercoat layer coating solution can be prepared by dispersing (α), (β), (γ), a binder resin (organic resin) and a solvent. It is also possible to prepare by subjecting (α), (β) and (γ) to a dispersion treatment, adding a liquid in which a binder resin (organic resin) is dissolved to the dispersion treatment, and further performing a dispersion treatment.
Examples of the solvent used for the undercoat layer coating liquid include alcohol-based, ketone-based, ether-based, ester-based, halogenated hydrocarbon-based, and aromatic-based organic solvents.
Examples of the dispersion treatment method include a method using a homogenizer, a paint shaker, an ultrasonic disperser, a ball mill, a sand mill, a roll mill, a vibration mill, an attritor, and a liquid collision type high speed disperser.

For the purpose of adjusting the surface roughness and transmittance of the undercoat layer and reducing cracks in the undercoat layer, the coating liquid for the undercoat layer may contain organic resin fine particles and a leveling agent, if necessary. .. Examples of the organic resin particles include hydrophobic organic resin particles such as silicone particles and hydrophilic organic resin particles such as crosslinked polymethacrylate resin (PMMA) particles.

Examples of the coating method for the undercoat layer coating liquid include a dip coating method (dipping coating method), a spray coating method, a spinner coating method, a bead coating method, a Meyer bar coating method, a blade coating method and a beam coating method. To be
Examples of the method for drying the coating film of the coating liquid for the undercoat layer include heat drying and blast drying.

The thickness of the undercoat layer is preferably 0.5 μm or more and 30 μm or less, more preferably 1 μm or more and 25 μm or less.

As described above, the electrophotographic photoreceptor of the present invention has a support, an undercoat layer on the support, and a photosensitive layer on the undercoat layer.
The photosensitive layer may be a single-layer type photosensitive layer containing a charge generating substance and a charge transporting substance in a single layer, or a charge transporting layer containing the charge transporting substance and a charge generating substance containing the charge generating substance. It may be a function-separated type (multilayer type) photosensitive layer which is functionally separated into layers. From the viewpoint of electrophotographic characteristics, a function-separated (laminated) photosensitive layer is preferable, and a function-separated (laminated) photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the support side is more preferable. Further, if necessary, a protective layer may be provided on the photosensitive layer.

As the support, one having conductivity (conductive support) is preferable.
As the support (conductive support), for example, a support made of metal (made of alloy) such as aluminum, aluminum alloy, stainless steel, nickel can be used. Alternatively, a metal (alloy) support or a plastic support having a layer formed by vacuum deposition of aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can be used. It is also possible to use a support obtained by impregnating plastic or paper with carbon black, tin oxide particles, titanium oxide particles, silver particles, or the like, or a plastic support having a conductive resin.
Examples of the shape of the support include a cylindrical shape and a belt shape. Among these shapes, the cylindrical shape is preferable.

The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment or the like for the purpose of suppressing interference fringes due to scattering of laser light.

A conductive layer may be provided between the support and the undercoat layer for the purpose of suppressing interference fringes due to scattering of laser light and covering scratches on the support.
The conductive layer can be formed by dispersing conductive particles such as carbon black and metal oxide particles in a binder resin.
The thickness of the conductive layer is preferably 5 μm or more and 40 μm or less, and more preferably 10 μm or more and 30 μm or less.

The undercoat layer according to the present invention is provided between the support or the conductive layer and the photosensitive layer (charge generation layer, charge transport layer).

As the charge generating substance used in the photosensitive layer, for example,
Azo pigments such as monoazo, disazo and trisazo,
Phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine,
Indigo pigments such as indigo, thioindigo,
Perylene anhydride, perylene pigments such as perylene imide,
Polycyclic quinone pigments such as anthraquinone, pyrenequinone, dibenzpyrenequinone,
Squarylium dye,
Pyrylium salt and thiapyrylium salt,
Triphenylmethane dye,
Quinacridone pigment,
Azurenium salt pigment,
Cyanine pigments such as quinocyanine,
Antoanthrone pigment,
Pyrantrone pigment,
Xanthene dye,
Quinone imine dye,
Examples include styryl dyes.

Among these, phthalocyanine pigments and azo pigments are preferable from the viewpoint of sensitivity, and among these, phthalocyanine pigments are particularly preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferable from the viewpoint of charge generation efficiency.
These charge generating substances may be used alone or in combination of two or more.

When the photosensitive layer is a laminate type, as the binder resin for the charge generation layer, for example, acrylic resin, allyl resin, alkyd resin, epoxy resin, diallyl phthalate resin, styrene-butadiene copolymer, butyral resin, benzal resin, poly Acrylate, polyacetal, polyamideimide, polyamide, polyallyl ether, polyarylate, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, polyvinyl acetal, polybutadiene, polypropylene, methacrylic resin, urea resin, vinyl chloride-vinyl acetate copolymer, Examples thereof include vinyl acetate resin and vinyl chloride resin. Among these, butyral resin is particularly preferable.
These resins may be used alone or as a mixture or a copolymer, and one kind or two or more kinds may be used.

The charge generation layer can be formed by applying a charge generation layer coating liquid obtained by dispersing a charge generation substance together with a binder resin and a solvent to form a coating film, and drying the coating film. ..
Examples of the dispersion treatment method include a method using a homogenizer, a paint shaker, an ultrasonic disperser, a ball mill, a sand mill, a roll mill, a vibration mill, an attritor, and a liquid collision type high speed disperser.
The ratio of the charge generating substance to the binder resin in the charge generating layer (charge generating substance: binder resin) is preferably in the range of 0.3:1 to 10:1 by mass ratio.

The solvent used in the coating liquid for the charge generation layer is preferably selected from the solubility and dispersion stability of the binder resin and the charge generation substance used in the charge generation layer. Examples of the solvent include organic solvents such as alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons and aromatic compounds.

The thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.1 μm or more and 2 μm or less.
The charge generation layer may contain various sensitizers, antioxidants, ultraviolet absorbers and plasticizers, if necessary.

Examples of the charge transport material used in the photosensitive layer include triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, butadiene compounds and the like.
Among these, triarylamine compounds are preferable from the viewpoint of charge mobility.

When the photosensitive layer is a laminated type, examples of the binder resin for the charge transport layer include acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, phenol resin, phenoxy resin, polyacrylamide, and polyamide. Examples thereof include imide, polyamide, polyallyl ether, polyarylate, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polysulfone, polyphenylene oxide, polybutadiene, polypropylene and methacrylic resin. Among these, polyarylate and polycarbonate are particularly preferable.
These resins may be used alone or as a mixture or a copolymer, and one kind or two or more kinds may be used.

The charge transport layer can be formed by applying a charge transport layer coating liquid obtained by dissolving a charge transport substance and a binder resin in a solvent to form a coating film, and drying the coating film.
The ratio of the charge transport material to the binder resin in the charge transport layer (charge transport material:binder resin) is preferably in the range of 0.3:1 to 10:1 by mass ratio. In addition, the drying temperature of the coating film is preferably 60° C. or higher and 150° C. or lower, and more preferably 80° C. or higher and 120° C. or lower, from the viewpoint of suppressing cracks. The drying time of the coating film is preferably 10 minutes or more and 60 minutes or less.

Examples of the solvent used for the charge transport layer coating liquid include, for example,
Alcohols such as propanol and butanol (especially alcohols with 3 or more carbon atoms),
Aromatic hydrocarbons such as anisole, toluene, xylene, chlorobenzene,
Examples thereof include alkylcycloalkanes such as methylcyclohexane and ethylcyclohexane.

Further, when the charge transport layer has a laminated structure, the charge transport layer on the surface side of the electrophotographic photosensitive member is preferably the following layer.
That is, in order to increase the mechanical strength of the electrophotographic photosensitive member, it is preferable to form a layer that is cured by polymerizing and/or crosslinking a charge transporting substance having a chain-polymerizable functional group.
Examples of the chain-polymerizable functional group include an acryloyloxy group, an alkoxysilyl group, and an epoxy group.
In order to polymerize and/or crosslink the charge transport substance having a chain-polymerizable functional group, heat, light, radiation (electron beam etc.) can be used.

When the charge transport layer of the electrophotographic photoreceptor is a single layer, the thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less, and more preferably 8 μm or more and 30 μm or less.

When the charge transport layer has a laminated structure of two layers, the thickness of the charge transport layer on the support side of the electrophotographic photoreceptor is preferably 5 μm or more and 30 μm or less, and the charge transport layer on the surface side of the electrophotographic photoreceptor is preferable. The film thickness of is preferably 1 μm or more and 10 μm or less.

The charge transport layer may contain various antioxidants, ultraviolet absorbers, plasticizers and the like, if necessary.

A protective layer intended to protect the photosensitive layer may be provided on the photosensitive layer.
The protective layer can be formed by applying a protective layer coating solution obtained by dissolving the above-mentioned various binder resins in a solvent to form a coating film, and drying the coating film.
In addition, the protective layer may be formed by applying a protective layer coating solution obtained by dissolving a resin monomer or oligomer in a solvent to form a coating film, and curing and/or drying the coating film.
Light, heat, or radiation (such as an electron beam) can be used to cure the coating film.

The thickness of the protective layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 7 μm or less.
The protective layer may contain conductive particles and the like, if necessary.

Examples of the method for applying the coating liquid for each of the above layers include dip coating method (dip coating method), spray coating method, spinner coating method, bead coating method, roller coating method, Mayer bar coating method, blade coating method, and beam coating. Methods such as the law can be mentioned.

The outermost layer (surface layer) of the electrophotographic photosensitive member may contain a lubricant such as silicone oil, wax, polytetrafluoroethylene particles, silica particles, alumina particles, and boron nitride.

The process cartridge of the present invention integrally supports the electrophotographic photosensitive member of the present invention and at least one means selected from the group consisting of charging means, developing means, transfer means and cleaning means, and an electrophotographic apparatus It is characterized by being removable from the main body.

The electrophotographic apparatus of the present invention is characterized by including the electrophotographic photosensitive member of the present invention, and a charging unit, an exposing unit, a developing unit and a transferring unit.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these. In addition, "part" in an Example means a "mass part", and "%" means the "mass %."

(Example 1)
(Surface treatment of metal oxide)
100 parts of zinc oxide particles (specific surface area: 19 m ² /g, powder resistance: 4.7×10 ⁶ Ω·cm) were stirred and mixed with 500 parts of toluene. To this, 0.8 part of a silane coupling agent (compound name: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 6 hours. .. Then, toluene was distilled off under reduced pressure, and the mixture was heated at 130° C. for 6 hours and dried to obtain surface-treated zinc oxide particles.

(Production of electrophotographic photoreceptor)
An aluminum cylinder having a diameter of 30 mm and a length of 357.5 mm was used as the support (conductive support).
80 parts of the surface-treated zinc oxide particles, 0.8 part of the compound represented by the formula (1-1), 1.6 parts of a 1% methyl ethyl ketone solution of the compound represented by the formula (2-1), a curing agent 15 parts of blocked isocyanate (trade name: Sumijour 3175, manufactured by Sumika Bayer Urethane Co., Ltd.) and polyvinyl butyral resin as a polyol resin (trade name: S-REC BM-1, manufactured by Sekisui Chemical Co., Ltd.) 15 parts were mixed with a mixed solvent of 72 parts of methyl ethyl ketone and 72 parts of 1-butanol. This was placed in a sand mill apparatus using glass beads having a diameter of 0.8 mm, and was subjected to dispersion treatment for 3 hours in an atmosphere of 23±3°C. After the dispersion treatment, 0.01 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) and crosslinked polymethylmethacrylate (PMMA) particles (trade name: Techpolymer SSX-103, Sekisui) 5.6 parts by Chemicals Industry Co., Ltd.) was added and stirred to prepare a coating liquid for the undercoat layer.
This coating liquid for undercoat layer was applied onto the support by dip coating to form a coating film, and the coating film was dried for 40 minutes at 160° C. to form an undercoat layer having a film thickness of 18 μm.

を、シクロヘキサノン１００部にポリビニルブチラール（商品名：エスレックＢＸ−１、積水化学工業（株）製）２部を溶解させた液に加えた。その後、これを、直径１ｍｍのガラスビーズを用いたサンドミルに入れ、２３±３℃の雰囲気下で１時間分散処理した。分散処理後、これに、酢酸エチル１００部を加えることによって、電荷発生層用塗布液を調製した。
この電荷発生層用塗布液を上記下引き層上に浸漬塗布して塗膜を形成し、該塗膜を１０分間９０℃で乾燥させることによって、膜厚が０．１９μｍの電荷発生層を形成した。 Next, 4 parts of a crystalline form of hydroxygallium phthalocyanine crystal (charge-generating substance) having strong peaks at Bragg angles 2θ±0.2° of 7.4° and 28.1° in CuKα characteristic X-ray diffraction, and 0.04 part of the compound represented by the formula (A)

Was added to a solution in which 100 parts of cyclohexanone and 2 parts of polyvinyl butyral (trade name: S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) were dissolved. Then, this was placed in a sand mill using glass beads having a diameter of 1 mm, and subjected to a dispersion treatment for 1 hour under an atmosphere of 23±3°C. After the dispersion treatment, 100 parts of ethyl acetate was added thereto to prepare a charge generation layer coating liquid.
The coating solution for a charge generation layer is applied onto the undercoat layer by dip coating to form a coating film, and the coating film is dried at 90° C. for 10 minutes to form a charge generation layer having a thickness of 0.19 μm. did.

ポリカーボネート樹脂（商品名：ユーピロンＺ４００、三菱エンジニアリングプラスチックス（株）製、ビスフェノールＺ型のポリカーボネート）１００部、および、下記式（Ｅ）で示される構造単位を有するポリカーボネート（粘度平均分子量Ｍｖ：２００００）０．０２部

を、クロロベンゼン６００部およびジメトキシメタン２００部の混合溶剤に溶解させることによって、電荷輸送層用塗布液を調製した。
この電荷輸送層用塗布液を上記電荷発生層上に浸漬塗布して塗膜を形成し、該塗膜を３０分間１００℃で乾燥させることによって、膜厚が２１μｍの電荷輸送層を形成した。 Next, 60 parts of the compound represented by the following formula (B) (charge-transporting substance), 30 parts of the compound represented by the following formula (C) (charge-transporting substance), 10 parts of the compound represented by the following formula (D),

100 parts of a polycarbonate resin (trade name: Iupilon Z400, Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type polycarbonate), and a polycarbonate having a structural unit represented by the following formula (E) (viscosity average molecular weight Mv: 20000) 0.02 copy

Was dissolved in a mixed solvent of 600 parts of chlorobenzene and 200 parts of dimethoxymethane to prepare a coating solution for the charge transport layer.
The coating solution for a charge transport layer was applied onto the charge generation layer by dip coating to form a coating film, and the coating film was dried at 100° C. for 30 minutes to form a charge transport layer having a film thickness of 21 μm.

１，１，２，２，３，３，４−ヘプタフルオロシクロペンタン３０部、および、１−プロパノール３０部を加え、ポリフロンフィルター（商品名：ＰＦ−０４０、アドバンテック東洋（株）製）で濾過を行うことによって、保護層用塗布液を調製した。
この保護層用塗布液を上記電荷輸送層上に浸漬塗布して塗膜を形成し、該塗膜を５分間５０℃で乾燥させた。乾燥後、窒素雰囲気下にて、加速電圧６０ｋＶ、吸収線量８０００Ｇｙの条件で１．６秒間電子線を該塗膜に照射した。その後、窒素雰囲気下にて、該塗膜の温度が１３０℃になる条件で１分間加熱処理を行った。なお、電子線の照射から１分間の加熱処理までの酸素濃度は２０ｐｐｍであった。次に、大気中において、該塗膜が１１０℃になる条件で１時間加熱処理を行うことによって、膜厚５μｍである保護層（第二の電荷輸送層）を形成した。
このようにして、支持体上に下引き層、電荷発生層、電荷輸送層および保護層を有する電子写真感光体を製造した。 Next, 1.5 parts of a fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) was added to 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: It was dissolved in a mixed solvent of 45 parts of Zeolora H, manufactured by Nippon Zeon Co., Ltd. and 45 parts of 1-propanol. After that, a liquid obtained by adding 30 parts of polytetrafluoroethylene particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) to the high pressure disperser (trade name: Microfluidizer M-110EH, US Microfluidics). (Manufactured by Co., Ltd.) to obtain a dispersion liquid. Then, 70 parts of a compound (hole transporting compound) represented by the following formula (F) was added to the dispersion liquid:

30 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 30 parts of 1-propanol were added, and a polyflon filter (trade name: PF-040, manufactured by Advantech Toyo Corp.) was used. The coating liquid for protective layer was prepared by performing filtration.
The coating liquid for protective layer was applied onto the charge transport layer by dip coating to form a coating film, and the coating film was dried at 50° C. for 5 minutes. After drying, in a nitrogen atmosphere, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 60 kV and an absorbed dose of 8000 Gy. Then, under a nitrogen atmosphere, heat treatment was performed for 1 minute under the condition that the temperature of the coating film was 130°C. The oxygen concentration from the electron beam irradiation to the heat treatment for 1 minute was 20 ppm. Then, in the air, heat treatment was performed for 1 hour under the condition that the coating film was 110° C. to form a protective layer (second charge transport layer) having a film thickness of 5 μm.
In this way, an electrophotographic photoreceptor having an undercoat layer, a charge generation layer, a charge transport layer and a protective layer on a support was produced.

(Example 2)
In Example 1, the amount of the compound represented by the formula (1-1) used was changed to 0.04 part, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was adjusted to 0. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 08 parts.

(Example 3)
In Example 1, the amount of the compound represented by the formula (1-1) used was changed to 0.16 part, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was adjusted to 0. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 32 parts.

(Example 4)
In Example 1, the amount of the compound represented by the formula (1-1) used was changed to 2.4 parts, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was changed to 4. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content was changed to 8 parts.

(Example 5)
In Example 1, the amount of the compound represented by the formula (1-1) used was changed to 4.0 parts, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was adjusted to 8. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content was changed to 0 part.

(Example 6)
An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) was changed to 0.64 parts. ..

(Example 7)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was changed to 8.0 parts. ..

(Example 8)
An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the amount of the 1% methyl ethyl ketone solution of the compound represented by the above formula (2-1) was changed to 16.0 parts. ..

(Example 9)
In Example 1, the amount of the compound represented by the formula (1-1) used was changed to 0.04 part, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was adjusted to 0. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 032.

(Example 10)
In Example 1, 0.8 part of the compound represented by the above formula (1-1) was changed to 0.16 part of the compound represented by the above formula (1-3) to give the compound represented by the above formula (2-1). The amount of 1% methyl ethyl ketone solution of the compound used was changed to 0.64 parts. An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 except for those.

(Example 11)
In Example 10, the amount of the compound represented by the formula (1-3) used was changed to 1.6 parts, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-1) used was 6. An electrophotographic photosensitive member was produced in the same manner as in Example 10 except that the amount was changed to 4 parts.

(Example 12)
In Example 1, 0.8 part of the compound represented by the above formula (1-1) was changed to 1.6 parts of the compound represented by the above formula (1-4) to give the compound represented by the above formula (2-1). The amount of 1% methyl ethyl ketone solution of the compound used was changed to 6.4 parts. An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 except for those.

(Example 13)
In Example 1, except that 1.6 parts of a 1% methyl ethyl ketone solution of the compound represented by the above formula (2-1) was changed to 3.2 parts of a 1% methyl ethyl ketone solution of the compound represented by the above formula (2-2). In the same manner as in Example 1, an electrophotographic photosensitive member was manufactured.

(Example 14)
In Example 13, the amount of the compound represented by the formula (1-1) used was changed to 0.04 part, and the amount of the 1% methyl ethyl ketone solution of the compound represented by the formula (2-2) used was adjusted to 0. An electrophotographic photosensitive member was produced in the same manner as in Example 13 except that the amount was changed to 032.

(Example 15)
In Example 1, the compound represented by the formula (1-1) was changed to the compound represented by the formula (1-12), and the compound represented by the formula (2-1) was replaced by the compound represented by the formula (2-3). An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound shown in (4) was used.

(Example 16)
An electrophotographic photosensitive member was produced in the same manner as in Example 15, except that the amount of the 1% methyl ethyl ketone solution of the compound represented by the above formula (2-3) was changed to 8.0 parts. ..

(Example 17)
In Example 15, the amount of the compound represented by the formula (1-12) used was changed to 0.04 part, and the amount of the 1% methylethylketone solution of the compound represented by the formula (2-3) used was adjusted to 0. An electrophotographic photosensitive member was produced in the same manner as in Example 15 except that the amount was changed to 032.

(Comparative Example 1)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the 1% methyl ethyl ketone solution of the compound represented by the above formula (2-1) was not used.

(Comparative example 2)
An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the compound represented by the formula (1-1) was not used.

(Comparative example 3)
An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the compound represented by the above formula (2-1) was changed to the compound represented by the following formula (G).

(Comparative example 4)
An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the compound represented by the above formula (1-1) was changed to the compound represented by the following formula (H).

[Electrical property evaluation of electrophotographic photoreceptor]
As an evaluation apparatus (evaluation electrophotographic apparatus), a remodeled machine of a copying machine (trade name: imageRUNNER iR-ADV C5051) manufactured by Canon Inc. was used. The evaluation device was installed in an environment of a temperature of 23° C. and a humidity of 50% RH. The surface potential of the electrophotographic photosensitive member was measured by removing the developing cartridge from the evaluation device and inserting the potential measuring device therein. The potential measuring device is configured by disposing a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe is at the center of the electrophotographic photosensitive member in the generatrix direction.
The electrophotographic photoconductors produced in Examples 1 to 17 and Comparative Examples 1 to 4 used for the measurement were allowed to stand for 3 days in an environment of temperature 50° C./humidity 95% RH, and temperature 23° C./humidity 50. After leaving it in the %RH environment overnight, it was set in the evaluation device.
As the charging condition, the applied voltage was adjusted so that the initial dark portion potential was −800V. As the exposure conditions, the laser light amount was adjusted so that the initial bright portion potential (VLa) in the 780 nm laser exposure irradiation was −200V.
The developing cartridge was attached to the above-mentioned evaluation apparatus, and the electrophotographic photosensitive member capable of continuously outputting 20,000 images was repeatedly used. After outputting 20,000 images, it was left for 5 minutes, the developing cartridge was replaced with a potential measuring device, and the light potential (VLb) of each electrophotographic photosensitive member after repeated use was measured. The potential of each electrophotographic photosensitive member was measured under the initially set charging and exposure conditions. The difference between the bright portion potential and the initial bright portion potential after repeated use of each electrophotographic photosensitive member was determined as the light portion potential fluctuation amount (ΔVL=|VLb|−|VLa|). The evaluation results are shown in Table 1.

As shown in Table 1, the electrophotographic photosensitive member of the example according to the present invention was used in a high temperature and high humidity environment for a while as compared with the electrophotographic photosensitive member of the comparative example not containing (β) or (γ). Deterioration of electrical characteristics after repeated use is suppressed.

Claims (9)

An electrophotographic photoreceptor having a support, an undercoat layer on the support, and a photosensitive layer on the undercoat layer,
The undercoat layer is
(Α) metal oxide particles,
(Β) a compound represented by the following formula (1), and

(In the formula (1), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. One or two of R ^{6 to} R ¹⁰ are hydroxy groups, and three or more of R ^{6 to} R ¹⁰ are not hydroxy groups.)
(Γ) Compound represented by the following formula (2)

(In the formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. . A ¹ represents an alkenyl group having 2 to 4 carbon atoms.)
An electrophotographic photosensitive member comprising: The electrophotographic photosensitive member according to claim 1, wherein the (α) contains zinc oxide particles. The said ((beta)) contains the compound shown by the said Formula (1), and two adjacent two of R< ⁶ >-R< ¹⁰ > in the said Formula (1) is a hydroxy group. Electrophotographic photoreceptor. The electrophotography according to claim 1, wherein the (γ) includes a compound represented by the formula (2) and A ¹ in the formula (2) is a 1-propenyl group. Photoconductor. An electrophotographic photosensitive member according to any one of claims 1 to 4 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported, A process cartridge that can be attached to and detached from the body of a photographic device. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, and a charging unit, an exposing unit, a developing unit, and a transferring unit. In the method for producing an electrophotographic photoreceptor, which comprises a step of forming an undercoat layer on a support, and a step of forming a photosensitive layer on the undercoat layer,
The step of forming the undercoat layer,
(Α) metal oxide particles,
(Β) a compound represented by the following formula (1), and

(In the formula (1), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. One or two of R ^{6 to} R ¹⁰ are hydroxy groups, and three or more of R ^{6 to} R ¹⁰ are not hydroxy groups.)
(Γ) Compound represented by the following formula (2)

(In the formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an amino group. . A ¹ represents an alkenyl group having 2 to 4 carbon atoms.)
A step of forming an undercoat layer by applying a coating liquid for an undercoat layer containing the above on the support to form a coating film, and drying and/or curing the coating film. Method for manufacturing electrophotographic photoreceptor. The content of the (β) in the undercoat layer coating liquid is 0.1% by mass or more and 4.0% by mass or less with respect to the content of the (α) in the undercoat layer. 7. The method for producing an electrophotographic photosensitive member according to 7. The content of the (γ) in the coating liquid for the undercoat layer is 1.0% by mass or more and 15% by mass or less with respect to the content of the (β) in the undercoat layer. 8. The method for producing an electrophotographic photosensitive member according to item 8.