JP2003186212A - Electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having such properties as excellent photosensibility electrification and performance stability for repeated use and high wear resistance, causing no frictional noise with a cleaning blade and having practically sufficient electrical and mechanical performance without causing image failure such as toner filming. <P>SOLUTION: In the electrophotographic photoreceptor having a photosensitive layer containing at least a charge generating material, a charge transfer material and a binder resin on a conductive base body, the photosensitive layer contains as the binder resin: a polymer essentially comprising a structural unit expressed by specified formula [1]; a polymer comprising repeating units expressed by specified formula [2] and specified formula [3]; and a polymer essentially comprising a structural unit expressed by specified formula [4]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly durable electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as Se, CdS, and Zn0 have been used as photoconductive materials for electrophotographic photoreceptors, but they have problems such as toxicity and low printing durability. Due to problems with temperature characteristics, etc., in recent years, electrophotographic photoreceptors using organic photoconductive materials have been actively developed because they are pollution-free, have excellent film-forming properties, and have a wide selection range of materials. ing. As the constitution of such an organic photoreceptor, a layer in which a charge generating material is dispersed in a binder resin (charge generating layer) and a layer in which a charge transporting material is dispersed in a binder resin (charge transporting layer) are provided on a support. A laminated structure that is stacked in this order, a single layer structure in which both the charge generation material and the charge transport material are dispersed in a binder resin, the charge transport layer on the support,
Various configurations such as an inverted two-layer type in which charge generation layers are laminated in this order have been proposed. Among them, the function-separated type photoconductor, in which the charge transport layer is laminated on the charge generation layer as the photosensitive layer in this order, is excellent in electrophotographic characteristics and durability, has a high degree of freedom in material selection, and variously designed photoreceptor characteristics. It is widely used because it can be done.

However, the main problem with the organic photoconductors currently in practical use is durability, and among them, film abrasion during repeated use, and reduction and residual of the charging potential due to electrical and chemical changes of the film. There is a problem that characteristic changes such as an increase in potential are likely to occur. In other words, these are the processes of forming a latent image by charging and exposure, transferring a toner image to a transfer paper, and removing the residual toner on the surface of the photoconductor with a blade, etc. The main factors are that the printing durability of the paper is not sufficient and that the organic photoconductive compound in the film is modified or decomposed by light or ozone and nitrogen oxides exposed during the image forming process. The durability above is still limited.

The performance required of the electrophotographic photosensitive member in the image forming process is, for example, high surface potential when charged, high carrier retention rate, high photosensitivity, and characteristic fluctuation even under any environment. Less, also
High-strength film, excellent wear resistance in repeated use, high stability of properties throughout life, and more physically and chemically stable photoreceptor coating liquid to improve production efficiency. Is required. It can be said that the role of the binder resin forming the surface layer of the photoreceptor is very important for these requirements.

A bisphenol A type polycarbonate has been used as a binder for such a photoreceptor. However, the bisphenol A-type polycarbonate has a drawback that the solution thereof is likely to gel because the polymer has high crystallinity, and the coating solution becomes unusable in a short period of time. When a film is formed by coating,
Crystalline polycarbonate may be deposited on the surface of the film to reduce the yield, or toner may adhere to the deposited protrusions when used in a copying machine and cleaning may not be performed, resulting in image defects due to poor cleaning. Further, when the electrophotographic photoreceptor using the above bisphenol A type polycarbonate as a binder resin is used as a photoreceptor of an electrophotographic copying machine, the surface of the photosensitive layer is easily scratched by being rubbed in the developing step or the cleaning step, and the photosensitive layer is It has the drawback of being easily worn. Copolymers of bisphenol A type with other molecules have been investigated to solve these drawbacks, but they are still insufficient.

In order to solve such a drawback, there has been proposed a technique for improving durability by using a bisphenol Z type polycarbonate resin as a binder on the surface of the photosensitive layer (Japanese Patent Laid-Open No. 20768/1993). .
However, although the photoreceptor using the bisphenol Z-type polycarbonate resin as a binder has good printing durability and abrasion resistance, it has poor initial sensitivity and has a drawback that the residual potential increases when it is repeatedly used under high temperature and high humidity. is doing. In addition, a polycarbonate resin having a novel specific structure has been proposed (Patent Registration No. 2531852), and it has been considered to mix two or more kinds of resins in order to make up for the drawbacks. Examples thereof include bisphenol A and bisphenol Z (patent registration 1735565), symmetrical diols and asymmetric diols (JP-A-6-317917). However, with the recent trend toward smaller drum diameters and faster processes, it is necessary to improve the durability of the electrophotographic photosensitive member electrically, chemically and mechanically.

In order to improve the durability, it is important not only to improve the binder resin alone, but also to combine it with a charge transport material compatible with the binder resin. As an example, a polycarbonate Z resin (PCZ) is used as a binder resin, and a specific distyryl compound is used as a charge transport material (JP-A 1-3).
No. 2265), a polycarbonate resin having a specific structure is used as a binder resin, and a specific styryl compound is used as a charge transporting material (Patent Registration 3160772). However, image quality is deteriorated due to scratches and the like during repeated use. However, there are problems such as the occurrence of a phenomenon and a decrease in image density due to an increase in residual potential. From these things, the current situation,
A variety of binder resins for electrophotographic photoconductors have been energetically researched for the purpose of further improving resin properties and handling, and by combining an arbitrary charge transport material with a high-performance binder resin, excellent electrophotographic characteristics can be obtained. Efforts have been made to obtain an electrophotographic photosensitive member having a coating strength.

[0008]

The object of the present invention is, in terms of the characteristics of the electrophotographic photoreceptor, excellent in photosensitivity characteristics, charging characteristics, characteristic stability in repeated use, and in addition, good abrasion resistance and cleaning. It is an object of the present invention to provide an electrophotographic photosensitive member which does not generate frictional noise with a blade and has both practically sufficient electric performance and mechanical performance without image defects such as toner filming.

[0009]

Means for Solving the Problems As a result of intensive studies by the present inventors, a combination of binder resins which are mechanically excellent and have excellent compatibility without deteriorating electrical characteristics, Furthermore, the present invention has been completed by using a charge transport material that is chemically tough such as ozone resistance, which has excellent compatibility with these binder resins. That is, in the present invention, three specific polymers are used as the binder resin, the present invention further specifies the mixing ratio of the polymers, and the present invention also specifies the charge transport material and the charge generating material. Then, the present invention was completed by specifying the additive and applying it to the laminated photoreceptor.

With the above structure, an electrophotographic photosensitive member having both electrical durability and mechanical durability can be realized.

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photosensitive member of the present invention has a structure in which a photosensitive layer is provided on a conductive support, and the photosensitive layer 4 comprises a charge generating layer 5 as shown in FIG. A laminated type in which the charge transport layer 6 is laminated, a laminated type in which the charge transport layer 6 and the charge generation layer 5 are oppositely laminated as shown in FIG. 2, or a charge generation material 2 and charge are laminated on the photosensitive layer 4 ′ as shown in FIG. There is a single layer type containing the transport material 3. Further, as shown in FIGS. 3 and 4, an undercoat layer (intermediate layer) 8 may be provided between the conductive support 1 and the photosensitive layers 4 and 4 '.

As the conductive support 1, for example, aluminum, copper, brass, zinc, nickel, stainless steel, chromium, molybdenum, vanadium, indium, titanium,
Metals and alloy materials such as gold and platinum can be used. In addition, aluminum, aluminum alloys, tin oxide, polyester films vapor-deposited or coated with gold or indium oxide, paper and metal films, plastics containing conductive particles Paper, paper, plastic containing a conductive polymer, or the like can be used. These materials are
It is used after being processed into a cylindrical shape, a cylindrical shape, or a thin film sheet shape.

An undercoat layer (intermediate layer) 8 may be introduced between the conductive support 1 and the photosensitive layers 4 and 4 '. As the subbing layer, generally, an anodized aluminum film, an inorganic layer such as aluminum oxide, aluminum hydroxide, polyvinyl alcohol, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, polyamide, etc. An organic layer, or a metal such as aluminum, copper, tin, zinc, or titanium as an inorganic pigment in the organic layer, or zinc oxide, aluminum oxide,
Those containing conductive or semi-conductive fine particles such as metal oxides such as titanium oxide are generally used. As the crystal form of titanium oxide, there are anatase type, rutile type, amorphous and the like, and any of them may be used, or two or more kinds may be mixed. The surface of the titanium oxide particles is A
It is preferable to use those coated with a metal oxide such as 1 ₂ O ₃ and ZrO ₂ or a mixture thereof.

As the binder resin contained in the undercoat layer 8, resins such as polyvinyl alcohol, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide and polyamide can be used. Polyamide resin is preferably used. The reason for this is that, as the properties of the binder resin, dissolution or swelling in the solvent used when forming the photoreceptor layer on the undercoat layer does not occur, and the adhesiveness with the conductive support is excellent. This is because it is required to have characteristics such as flexibility. More preferably, an alcohol-soluble nylon resin can be used among the polyamide resins. For example, 6-nylon, 66
-Nylon, 610-Nylon, 11-Nylon, 12
There are so-called copolymerized nylon obtained by copolymerizing nylon and the like, and types such as N-alkoxymethyl-modified nylon and N-alkoxyethyl-modified nylon in which nylon is chemically modified.

In the present invention, a general organic solvent can be used as the organic solvent used in the coating liquid for the undercoat layer, but when a more preferable alcohol-soluble nylon resin is used as the binder resin, 1 to
4 lower alcohol groups and, for example, dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloropropane, toluene, tetrahydrofuran, 1,3-
It is preferable that the organic solvent is selected from the group consisting of other organic solvents such as dioxolane, and single and mixed organic solvents selected from the group consisting of: Here, by mixing the above organic solvent, the dispersibility of titanium oxide is improved as compared with the case of using the alcohol solvent alone, and the storage stability of the coating liquid can be prolonged and the coating liquid can be regenerated. Further, when forming a subbing layer by dipping and coating a conductive support in a subbing layer coating solution, coating defects and unevenness of the subbing layer are prevented, and a photosensitive layer formed thereon is made uniform. Since it can be applied, it is possible to form an electrophotographic photosensitive member having very excellent image characteristics without film defects.

As a method for producing the undercoat layer 8, a coating liquid for the undercoat layer is prepared by adding a solvent and a binder resin to the above-mentioned inorganic pigment and dispersing the mixture with a dispersing machine such as a ball mill, a Dyno mill or an ultrasonic oscillator. For a sheet, a baker applicator, a bar coater, casting, spin coating, etc. can be used, and for a drum, a spray method, a vertical ring method, a dip coating method, etc. can be used. The charge generation layer 5 is
The main component is a charge generating material that generates an electric charge by light irradiation, and if necessary, a known binder, plasticizer, and sensitizer are included. As the charge generation material, perylene imide, perylene pigments such as perylene anhydride, quinacridone, polycyclic quinone pigments such as anthraquinone, metal and metal-free phthalocyanines, phthalocyanine pigments such as halogenated metal-free phthalocyanines, squarylium dyes, Azurenium dye, thiapyrylium dye, and azo pigment having a carbazole skeleton, styrylstilbene skeleton, triphenylamine skeleton, dibenzothiophene skeleton, oxadiazole skeleton, fluorenone skeleton, bisstilbene skeleton, distyryloxadiazole skeleton or distyrylcarbazole skeleton Etc.

Examples of pigments having a particularly high charge generation ability include metal-free phthalocyanine pigments, oxotitanyl phthalocyanine pigments, bisazo pigments containing a fluorene ring and a fluorenone ring, bisazo pigments composed of aromatic amines, and trisazo pigments. It is possible to provide a photoreceptor having sensitivity. Furthermore, among the oxotitanyl phthalocyanines, the Bragg angle (2 °
The crystal form showing a diffraction peak at (± 0.2 °) 27.3 ° is more preferable because it has higher sensitivity.

The charge generating layer 5 may be produced by adding an organic solvent to the fine particles of these charge generating materials and then using a ball mill,
Sand grinder, paint shaker, using a coating liquid obtained by pulverizing and dispersing with an ultrasonic disperser, in the case of a sheet, a baker applicator, a bar coater,
In the case of a drum, such as casting and spin coating, it is prepared by a spray method, a vertical ring method, or a dip coating method. Also, as a binder resin to increase the binding property,
For example, polyester resin, polyvinyl acetate, polyacrylic acid ester, polycarbonate, polyarylate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, melamine resin, silicone resin, acrylic resin, cellulose ester, Various binder resins such as cellulose ether and vinyl chloride-vinyl acetate copolymer resin may be added. The film thickness is usually preferably 0.05 to 5 μm, and particularly preferably 0.1 to 1 μm. Further, the charge generation layer may optionally contain various additives such as a leveling agent, an antioxidant and a sensitizer for improving the coating property.

The charge transporting layer 6 provided on the charge generating layer 5 has a charge transporting material capable of receiving and transporting charges generated by the charge generating material and a binder as an essential component, and transporting the charge. Materials include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensation products and its derivatives, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, oxadiazole derivatives, Imidazole derivative, 9- (p-diethylaminostyryl) anthracene, 1,1-bis (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, pyrazoline derivative, phenylhydrazone, hydrazone derivative, triphenylamine compound , Tet Electron-donating substances such as phenyldiamine compounds, triphenylmethane compounds, stilbene compounds, azine compounds having a 3-methyl-2benzothiazoline ring, or fluorenone derivatives, dibenzothiophene derivatives, indenothiophene derivatives, phenanthrene Examples thereof include electron-accepting substances such as quinone derivatives, indenopyridine derivatives, thioxanthone derivatives, benzo [c] cinnoline derivatives, phenazine oxide derivatives, tetracyanoethylene, tetracyanoquinodimethane, promannyl, chloranil, and benzoquinone. Among them, the specific butadiene-based compound, styryl-based compound, and amine compound of the present invention having the following structures are more preferable in the present invention because the material itself has a high hole-transporting ability and can maintain high sensitivity even in a high resin ratio state. is there. An example is shown below.

Examples of the butadiene compound include compounds represented by the following structural formulas.

[0020]

[Chemical 8] [In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each represent an aryl group which may have a substituent, and Ar _{1 to} Ar _1
At least one of ₄ is an aryl group having a substituted amino group as a substituent. n represents 0 or 1. ]

Specific examples thereof include compounds represented by the following structural formulas 8 to 19.

[Chemical 9]

[0022]

[Chemical 10]

Examples of the styryl compound include compounds represented by the following structural formulas.

[Chemical 11] [In the formula, Ar ₅ represents an aryl group which may have a substituent, Ar ₆ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent, and R ₁₇ represents hydrogen. Represents an atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent,
Y represents an aryl group or the like which may have a substituent. ]

Specific examples include compounds represented by the following structural formulas 20 to 35.

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

Examples of amine compounds include compounds represented by the following structural formulas.

[Chemical 16] [In formula, R < ₁₈ > -R < ₂₃ > is a hydrogen atom, a halogen atom,
Alkyl group or alkoxy group, r and s are 1 to 4, p,
q, t, and u represent the integer of 1-5. ]

Specific examples thereof include compounds represented by the following structural formulas 36 to 41.

[Chemical 17]

[0030]

[Chemical 18]

The charge transport layer is formed by binding these charge transport materials with the three binder resins of the present invention. The binder resin represented by the general formula [1] is
Since the structure is asymmetric, it is difficult to crystallize, and since it does not have a bulky group, it can be densely packed when it is dried and dried from a solution, and a strong film can be formed, so that it has excellent wear resistance. On the other hand, since the binder resin represented by the repeating units of the general formulas [2] and [3] contains polyalkylsiloxane, it has a low surface friction resistance and can prevent the friction noise with the cleaning blade. Further, since the binder resin represented by the general formula [4] has a small gas permeability,
It is possible to prevent penetration of gases such as ozone and NOx that deteriorate the characteristics of the photoconductor. These resins have excellent compatibility with the charge transport material and also have excellent durability.

As for the molecular weight, from the viewpoints of the electrical characteristics of the photoconductor, the repeated stability, and the printing durability, the general formulas [1] and [2] are used.
The polycarbonate resin composed of the repeating unit [3] preferably has a viscosity average molecular weight of 30,000 to 70,000. When the viscosity average molecular weight is less than 30,000, the compatibility is high and the repeated stability of electric properties is excellent, but the printing durability is significantly deteriorated. When the viscosity average molecular weight is more than 70,000, the printing durability is improved, but the solution viscosity is high. Therefore, it takes a long time to mix with the charge transporting material, and unevenness of the coating film easily occurs, resulting in a decrease in productivity. On the other hand, the polycarbonate resin of the general formula [4] has a viscosity average molecular weight of 1
It is preferably 5,000 to 35,000. 1
When it is less than 5,000, the printing durability is significantly deteriorated, and 3
If it is more than 5,000, printing durability is improved, but
The initial sensitivity decreases, the residual potential increases after repeated use, and the image stability decreases significantly.

The mixing ratio of the polycarbonate resin composed of the repeating structural units of the general formulas [1] and [2] [3] is preferably 1: 9 to 9: 1. From this, the structure represented by the general formula [1] is obtained. When the amount of the resin containing the unit as the main component is small, the desired mechanical strength cannot be obtained and scratches are likely to occur. On the contrary, when the amount of the resin composed of the repeating structural units of the general formulas [2] and [3] is smaller than this, the frictional resistance increases and the friction noise with the cleaning blade is likely to occur. The resin containing the structural unit represented by the general formula [4] as a main component is 50 to 30 relative to the total amount of the polycarbonate resin composed of the repeating structural units of the general formulas [1] and [2] [3]. %, The desired mechanical strength cannot be obtained, and if less than this, halftone white spots and black bands are likely to occur in the image due to deterioration due to ozone and NOx.

The polymer composed of the repeating unit of the general formula [1] is a polycarbonate resin represented by the following structural formula.

[Chemical 19] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a carbon atom. It represents a cyclic hydrocarbon residue of formula 4 to 10, a substituted or unsubstituted aryl group, and L is an integer.)

Specific examples include polymers represented by the following chemical formulas 42 to 46.

[Chemical 20]

The polymer composed of the repeating units of the general formulas [2] and [3] is a polycarbonate resin represented by the following structural formula.

[Chemical 21] (In the formula, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ¹ is each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and each X independently represents an alkylene group having 2 or more carbon atoms or an alkyleneoxy group having 2 or more carbon atoms. Is an alkylene group,
X ′ is independently an alkylene group having 2 or more carbon atoms, an alkyleneoxyalkylene group having 2 or more carbon atoms, or an oxygen atom, a is each independently an integer of 0 to 4, and na is 0 or 1. nb is 1 or 2, nc is 1 or 2, provided that na + nb + nc = 3, n1, n
2, n3 and n4 are each independently an integer of 0 or 1 or more, provided that n1 + n2 + n3 + n4 = 0 to 450. )

[0037]

[Chemical formula 22] (In the formula, each R ² is independently a halogen atom, a vinyl group, an allyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and 3 carbon atoms. To a substituted or unsubstituted cycloalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, and a is independently 0 to Is an integer of 4,
Y is a single bond, -O-, -CO-, -S-, -SO-,-.
_{^{SO 2 -, - CR 3 R}} 4 -, a substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms, a substituted or unsubstituted 2 to 12 carbon atoms alpha, .omega. alkylene group, 9,9
Fluorenylidene group, 1,8-menthanediyl group, 2,
8-menthanediyl group, a substituted or unsubstituted pyrazilidene group or a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, provided that R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms, or It is an unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. )

When the polycarbonate resin is a polymer composed of the repeating units [2] and [3],
The molar ratio of the repeating unit general formula [2] and the repeating unit general formula [3] to the total of the repeating unit general formula [2], the general formula [2] / [the general formula [2] + the general formula [3]] is 0. It is preferably 0.0001 to 1, more preferably 0.0003 to 0.5, and particularly preferably 0.0.
005 to 0.3. In addition, the repeating unit general formula [2] and general formula [3] may each have 1 type (s) or 2 or more types. Further, this polycarbonate polymer,
The repeating units other than the general formula [2] and the general formula [3] may be contained within a range not hindering the achievement of the object of the present invention. In the general formula [2], the R group is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and examples of the monovalent hydrocarbon group include, for example, substituted with 1 to 6 carbon atoms. Or an unsubstituted alkyl group, having 6 to 6 carbon atoms
12 substituted or unsubstituted aryl groups may be mentioned.

Specific examples of the R group in the general formula [2] are as follows. The unsubstituted alkyl group having 1 to 6 carbon atoms is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a hexyl group, A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group and a tert-butyl group are preferable. The unsubstituted aryl group having 6 to 12 carbon atoms is a phenyl group, a naphthyl group or a biphenylyl group, and a phenyl group is preferable.

Specific examples of R ^{1 in} the general formula [2] are as follows. The unsubstituted alkyl group having 1 to 6 carbon atoms is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a hexyl group, A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group and a tert-butyl group are preferable. The halogen atom is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Examples of the unsubstituted alkoxy group having 1 to 6 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group,
Butyloxy group, 2-butyloxy group, tert-butyloxy group, isobutyloxy group, pentyloxy group,
It is a hexyloxy group, and a methyloxy group, an ethyloxy group, a propyloxy group, and an isopropyloxy group are preferable.

The unsubstituted aryl group having 6 to 12 carbon atoms is a phenyl group, a naphthyl group or a biphenylyl group, preferably a phenyl group. The alkylene group having 2 or more carbon atoms represented by X and X ′ in the general formula 2 has 2 to 2 carbon atoms.
The alkylene groups of 6 are mentioned, and they are an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and a hexamethylene group, and an ethylene group, a trimethylene group and a tetramethylene group are preferable.

Examples of the alkyleneoxyalkylene group having 2 or more carbon atoms represented by X and X'in the general formula [2] include alkyleneoxyalkylene groups having 4 to 10 carbon atoms, such as ethyleneoxypropylene group and ethyleneoxybutylene. Groups are preferred. In the general formula [3], R ² , Y,
Specific examples of R ³ and R ⁴ are as follows. The halogen atom represented by R ² is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Examples of the unsubstituted alkyl group having 1 to 10 carbon atoms represented by R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, isobutyl. A group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group and a tert-butyl group are preferable.

6 to 12 carbon atoms represented by R ² , R ³ and R ⁴
The unsubstituted aryl group is a phenyl group, a naphthyl group or a biphenylyl group, and a phenyl group is preferable. R
^The C3-C12 unsubstituted cycloalkyl group represented by ² includes a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and a cyclopentyl group and a cyclohexyl group are preferable.

The unsubstituted alkoxy group having 1 to 6 carbon atoms represented by R ² includes methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, 2-butyloxy group, tert-butyloxy group,
It is an isobutyloxy group, a pentyloxy group or a hexyloxy group, and a methyloxy group, an ethyloxy group, a propyloxy group or an isopropyloxy group is preferable. The unsubstituted aryloxy group having 6 to 12 carbon atoms represented by R ² is a phenyloxy group, a naphthyloxy group or a biphenylyloxy group, and a phenyloxy group is preferable. As the unsubstituted arylene group having 6 to 24 carbon atoms represented by Y,
It is a phenylene group, a naphthylene group, a biphenylylene group, a terphenylylene group, or a quarter phenylylene group, and a phenylene group is preferable.

Examples of the unsubstituted cycloalkylidene group having 5 to 11 carbon atoms represented by Y include a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclooctylidene group, a cyclononylidene group, a cyclodecylidene group, It is a cycloundecylidene group, and a cyclohexylidene group is preferable. Examples of the unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms represented by Y include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, Decamethylene group, undecamethylene group,
It is a dodecamethylene group, preferably an ethylene group and a trimethylene group.

The 1,8-menthanediyl group represented by Y is preferably a 1,8-p-menthanediyl group. The 2,8-menthanediyl group represented by Y is preferably a 2,8-p-menthanediyl group. Substituted alkyl group, substituted aryl group, substituted alkoxy group, substituted aryloxy group, substituted cycloalkyl group, substituted arylene group, substituted α, ω-
The alkylene group, a substituted cycloalkylidene group and a substituted pyrazylidene group are each an unsubstituted alkyl group, an unsubstituted aryl group, an unsubstituted alkoxy group, an unsubstituted aryloxy group, an unsubstituted cycloalkyl group, an unsubstituted arylene group, At least 1 on an unsubstituted α, ω-alkylene group and an unsubstituted cycloalkylidene group or an unsubstituted pyrazylidene group
It means a group in which one hydrogen atom is substituted with a substituent.

Substituents of the substituted alkyl group and the substituted alkoxy group include a halogen atom (fluorine, chlorine, bromine, iodine), an aryl group having 6 to 12 carbon atoms (phenyl, naphthyl, biphenylyl), and 1 to 4 carbon atoms. Alkoxy groups (methoxy, ethoxy, propoxy, isopropoxy,
Butoxy, sec-butoxy, tert-butoxy, isobutoxy), an alkylthio group having 1 to 4 carbon atoms (such as methylthio), and an arylthio group having 6 to 12 carbon atoms (such as phenylthio). As the substituent of the substituted aryl group, the substituted aryloxy group and the substituted arylene group, a halogen atom (fluorine, chlorine, bromine, iodine), a carbon number of 1 to 1
4 alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl), alkoxy groups having 1 to 4 carbon atoms (methoxy,
Ethoxy, propoxy, isopropoxy, butoxy, s
ec-butoxy, tert-butoxy, isobutoxy), an alkylthio group having 1 to 4 carbon atoms (such as methylthio), and an arylthio group having 6 to 12 carbon atoms (such as phenylthio).

The substituents of the substituted α, ω-alkylene group, the substituted cycloalkyl group, the substituted cycloalkylidene group and the substituted pyrazylidene group include a halogen atom (fluorine, chlorine,
Bromine, iodine), an alkyl group having 1 to 4 carbon atoms (methyl,
Ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl), carbon number 6 to 1
2 aryl groups (phenyl, naphthyl, biphenylyl), alkoxy groups having 1 to 4 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-
Butoxy, tert-butoxy, isobutoxy), alkylthio groups having 1 to 4 carbon atoms (methylthio etc.), 6 carbon atoms
~ 12 arylthio groups (such as phenylthio). In the case of R ² , R ³ and R ⁴ , a preferred example of the substituted alkyl group having 1 to 10 carbon atoms substituted with a halogen atom is a trifluoromethyl group in which three hydrogen atoms of a methyl group are substituted with fluorine atoms. Can be mentioned. General formula [2]
In the above, n1 and n2 are each independently an integer of preferably 1 to 20, and n3 + n4 is preferably an integer of 0 to 100. It is preferable that n1 + n2 + n3 + n4 = an integer of 2 to 100.

The polycarbonate polymer of the present invention includes, for example, a hydroxyphenyl group-containing polyorganosiloxane represented by the following general formula [8] and the following general formula:

It can be produced by reacting the dihydric phenol represented by [9] with a carbonic acid ester forming compound. Incidentally, in the production of the polycarbonate polymer of the present invention, the hydroxyphenyl group-containing polyorganosiloxane general formula [8] may be used alone or in combination of two or more, and a dihydric phenol may be used. General formula

[9] may be used alone or in combination of two or more.

[0050]

[Chemical formula 23] (In the formula, R, R ¹ , X, X ′, a, na, nb, nc,
n1, n2, n3 and n4 have the same meanings as described above. )

[0051]

[Chemical formula 24] (In the formula, R ² , a and Y have the same meanings as described above.) As a production method, for example, phosgene or the like is used as a carbonic acid ester-forming compound, and the hydroxyphenyl group is added in the presence of a suitable acid binder. Containing polyorganosiloxane general formula [8] and dihydric phenol general formula

A method of polycondensation with [9], a method of performing a transesterification reaction using bisaryl carbonate as a carbonic acid ester-forming compound, and the like are applicable. These reactions are carried out in the presence of an end terminating agent and / or a branching agent, if necessary.

Specific examples of the above-mentioned hydroxyphenyl group-containing polyorganosiloxane formula [8] include the following.

[Chemical 25]

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

The above-mentioned general formula [8] containing a hydroxyphenyl group-containing polyorganosiloxane can be prepared by reacting the following general formula [1] in the presence of a catalyst for hydrosilylation reaction such as a platinum catalyst.
0]

[Chemical 28] (In the formula, R, R ¹ , X, X ′, a, na, nb, nc,
n1, n2, n3 and n4 have the same meanings as described above. )
Addition reaction of a polyorganosiloxane having at least two silicon-bonded hydrogen atoms represented by and an aliphatic unsaturated bond-containing hydrocarbon compound having a phenol group whose hydroxyl group is protected by a triorganosilyl group in the molecule After that, a protecting group such as a triorganosilyl group can be produced by adding methanol or the like in the presence of an acid catalyst and heating to remove the protecting group. At this time, an aliphatic unsaturated bond-containing hydrocarbon compound having a phenol group whose hydroxyl group is not protected by a triorganosilyl group or the like can also be used.

Among the polyorganosiloxanes having at least two silicon atom-bonded hydrogen atoms represented by the above general formula [10], the polyorganosiloxane in which X ′ is alkylene or alkyleneoxyalkylene is, for example,
The following general formula [11]

[Chemical 29] (In the formula, R has the same meaning as described above, D is a hydrogen atom or a lithium atom, and n4 is an integer of 1 or more.), And an organosilane or polyorganosiloxane represented by the following general formula: [12]

[0057]

[Chemical 30] (In the formula, R, X ′, a, na, nb, nc, n1, n2
And n3 have the same meanings as described above, and Hal is a halogen atom. It can be produced by subjecting a siloxane represented by the formula (4) to a condensation reaction (JP-A-4-3535).
23). Among the polyorganosiloxanes having at least two silicon-bonded hydrogen atoms represented by the above general formula [10], the polyorganosiloxane in which X ′ is an oxygen atom is represented by, for example, the following general formula [13]. With organosilane or polyorganosiloxane,
It can be produced by subjecting a siloxane represented by the following general formula [14] to a condensation reaction.

[0058]

[Chemical 31] (In the formula, D, Hal, R, na, nb, nc, n1, n
2 and n3 have the same meanings as above. )

General formula

Examples of the dihydric phenol represented by [9] include, for example, 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-3,3. '-Dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'
-4,4'- such as dicyclohexylbiphenyl, 4,4'-dihydroxy-3,3'-divinylbiphenyl, 3,3'-diallyl-4,4'-dihydroxybiphenyl
Dihydroxybiphenyls; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-
Hydroxyphenyl) -1-phenylmethane, bis (4
-Hydroxy-3-methylphenyl) methane, bis (4
-Hydroxy-3-nonylphenyl) methane, bis (4
-Hydroxy-3,5-dimethylphenyl) methane,

1,1-bis (2-tert-butyl-4)
-Hydroxy-5-methylphenyl) -1-phenylmethane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3-fluoro-4-hydroxyphenyl)
Methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (4-hydroxy-3-vinylphenyl) methane, bis (3-allyl-4-hydroxyphenyl) methane, bis (4-hydroxy-5) -Methyl-3
-Vinylphenyl) methane, bis (3-allyl-4-hydroxy-5-methylphenyl) methane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-
4-hydroxyphenylmethane, bis (2-hydroxy-4-methylphenyl) methane, bis (6-tert-)
Butyl-2-hydroxy-4-methylphenyl) methane,

Bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl)
-1-Phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1
-Bis (4-hydroxy-3-phenylphenyl) -1
-Phenylethane, 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-tert-butyl-
4-hydroxy-3-methylphenyl) ethane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-4)
-Methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxy-2-methylphenyl) propane,

1,1-bis (2-tert-butyl-4)
-Hydroxy-5-methylphenyl) propane, 2,2
-Bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (alias: tetrafluorobisphenol A), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane (alias: tetrachloro) Bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (alias: tetrabromobisphenol A),

2,2-bis (3-bromo-5-chloro-)
4-hydroxyphenyl) propane, 2,2-bis (3
-Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2-bis (4
-Hydroxy-3-vinylphenyl) propane, 2,2
-Bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-5-methyl-3-)
Vinylphenyl) propane, 2,2-bis (3-allyl-4-hydroxy-5-methylphenyl) propane,
2,2-bis (2-hydroxy-4,6-dimethylphenyl) propane, 2,2-bis (4-sec-butyl-)
2-hydroxyphenyl) propane, 1,1-bis (2
-Tert-butyl-5-methyl-4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane,

2,2-bis (4-hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (2-butyl-4-hydroxy-5-methyl) Phenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (4-hydroxy-2)
-Methyl-5-tert-pentylphenyl) butane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-bibromo-4-)
Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,
2-bis (4-hydroxyphenyl) pentane, 1,1
-Bis (4-hydroxyphenyl) cyclopentane,
2,2-bis (4-hydroxyphenyl) hexane, 2
-Ethyl-1,1-bis (4-hydroxyphenyl) hexane,

4,4-bis (4-hydroxyphenyl)
Heptane, 1,1-bis (2-tert-butyl-4-
Hydroxy-5-methylphenyl) heptane, 2,2-
Bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4- Hydroxy-3-cyclohexylphenyl) cyclohexane,
1,1-bis (4-hydroxy-3-vinylphenyl)
Cyclohexane, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-
Hydroxy-5-methyl-3-vinylphenyl) cyclohexane, 1,1-bis (3-allyl-4-hydroxy-5-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane Bis (hydroxyphenyl) alkanes such as;

Bis (4-hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) Bis (4-hydroxyphenyl) sulfides such as -3-methylphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (4-
Bis (4-hydroxyphenyl) sulfoxides such as hydroxy-3-methylphenyl) sulfoxide; bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxy-3-) Bis (4-hydroxyphenyl) sulfones such as phenylphenyl) sulfone; Bis (hydroxyphenyl) ketones such as 4,4′-dihydroxybenzophenone;

9,9-bis (4-hydroxyphenyl)
Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3-ethyl-
4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9,9-bis (4-hydroxy-3-vinylphenyl) fluorene, 9,9-bis (3-allyl -4-Hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-5-methyl-3-vinylphenyl) fluorene, 9,9-bis (3-allyl-4-hydroxy-5-
Bis (hydroxyphenyl) fluorenes such as methylphenyl) fluorene; dihydroxy-p-terphenyls such as 4,4 ″ -dihydroxy-p-terphenyl;

Dihydroxy-p-quaterphenyls such as 4,4 "-dihydroxy-p-quaterphenyl; 2,5-bis (4-hydroxyphenyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3 , 6
-Bis (hydroxyphenyl) pyrazines such as dimethylpyrazine and 2,5-bis (4-hydroxyphenyl) -2,6-diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (4-Hydroxy-3-methylphenyl) menthane, 1,8-bis (4
Bis (4-hydroxyphenyl) menthanes such as -hydroxy-3,5-dimethylphenyl) menthane; and the like.

In addition, the general formula

These dihydric phenols represented by [9]

Besides [9], dihydroxybenzenes such as hydroquinone, resorcinol, catechol and methylhydroquinone; 1,3-dihydroxynaphthalene, 1,
4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-
Dihydroxynaphthalene such as dihydroxynaphthalene; Dihydroxybisindane such as 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylbisindane; 1,4-bis [2- (4-hydroxyphenyl) −
2-Propyl] benzene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene and the like can also be used.

Among these various dihydric phenols, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ) −
1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) ) Propane, 2,2-bis (4-hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone, Two
2'-bis (4-hydroxy-3-methoxyphenyl)
-1,1,1,3,3,3-hexafluoropropane and the like are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

The polymer composed of the repeating unit of the general formula [4] is a polycarbonate resin represented by the following structural formula.

[Chemical 32] (In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R
¹⁴ , R ¹⁵ and R ¹⁶ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon residue having 4 to 10 carbon atoms, a substituted or unsubstituted aryl group. . Z is a group of atoms necessary for forming a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocycle. m is an integer. )

Specific examples include the compounds represented by the following chemical formulas 54 to 58.

[Chemical 33]

Further, as a solvent for dissolving these materials,
Alcohols such as methanol and ethanol, acetone,
Ketones such as methyl ethyl ketone and cyclohexanone,
Ethers such as ethyl ether and tetrahydrofuran,
Aliphatics such as chloroform, dichloroethane, dichloromethane, halogenated hydrocarbons, benzene, chlorobenzene,
There are aromatics such as toluene. The charge transport material / binder resin ratio is usually about 10/5 to 10/25, but in the present invention, it is 10/14 to 1 from the viewpoint of improving wear resistance.
0/20 is preferred. The charge transport layer coating liquid of the present invention contains additives such as a plasticizer, an antioxidant, an ultraviolet absorber, and a leveling agent in order to improve film-forming properties, flexibility, coating properties, and the like. Is also good.

When the amount of the charge transport material is more than 10/5, the sensitivity characteristics are good, but the charging characteristics, the mechanical strength of the film, the image stability against ozone and NOx generated in the charging process (HT white). 1)
On the contrary, when the amount of the binder resin is more than 0/20, the charging property, the mechanical strength and the image stability are good, but the sensitivity property is remarkably deteriorated. The thickness of the charge transport layer is about 1
It is from 0 to about 50 μm, preferably from about 10 to about 35 μm. As the antioxidant, an antioxidant generally used by adding it to a resin or the like can be used as it is. For example, vitamin E, hydroquinone, hindered amine, hindered phenol, paraphenylenediamine,
Aryl alkanes and their derivatives, organic sulfur compounds, organic phosphorus compounds and the like may be blended and used. Among them, hindered amines and hindered phenols can further improve the image stability against ozonosphere, NOx, etc. (HT white spots and black bands).

As the leveling agent, silicone oils or polymers or oligomers having a perfluoroalkyl group in the side chain can be used, and the amount used is preferably 0 to 1 part by weight per 100 parts by weight of the binder resin. The coating solution for the charge transport layer is generally a method in which the charge transport material, the binder resin and the additive are weighed and dissolved in a predetermined amount of an organic solvent at the same time without any problem. Among them, a method of adding a carrier transport material after dissolving it in a solvent and dissolving it is preferable. According to this method, the molecular dispersibility of the carrier-transporting material in the binder resin is improved, and the latent and local crystallization of the carrier-transporting agent in the film is suppressed, whereby the initial sensitivity is improved and repeated. Potential stability during use, good image characteristics, etc. are provided. As the coating method, the same methods as those for the undercoat layer and the charge generation layer are used. A suitable solvent for dissolving (or dispersing) the charge transport material is substantially the same as the solvent for dispersing the charge generating material, and can be selected from the solvents listed for the charge generating material. A particularly preferred solvent is tetrahydrofuran.

<Example> (Example 1) Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TT055)
A) 7 parts by weight and copolymerized nylon (manufactured by Toray Industries: CM800
0) 13 parts by weight of 159 parts by weight of methyl alcohol and 1,
In addition to 106 parts by weight of a mixed solvent of 3-dioxolane, dispersion treatment was carried out for 8 hours on a paint shaker to prepare a coating liquid for the intermediate layer. This coating liquid was filled in a coating tank, and an aluminum drum-shaped support having a diameter of 30 mm and a total length of 326.3 mm was immersed as a conductive support, pulled up, and naturally dried to form an intermediate layer having a film thickness of 1 μm.

In the X-ray diffraction spectrum, 1 part by weight of crystalline oxotitanyl phthalocyanine showing a diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 °,
Butyral resin (manufactured by Denki Kagaku Kogyo: # 6000-C)
1 part by weight was mixed with 98 parts by weight of methyl ethyl ketone and dispersed by a paint shaker to obtain a coating liquid for charge generation layer, which was applied onto the intermediate layer and air-dried to give a film thickness of 0.4 μm.
m charge generating layer was formed.

Then, a butadiene compound (T405, manufactured by Takasago Chemical Co., Ltd.) 1 represented by the structural formula of the exemplified compound [Chemical Formula 9] 1
00 parts by weight, a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 42] (viscosity average molecular weight 50,0
00) 40 parts by weight and a polycarbonate resin having a repeating unit represented by the following structural formula [Chemical formula 59] (viscosity average molecular weight 40,000) 40 parts by weight, a polycarbonate resin having a repeating unit represented by a structural formula [Chemical formula 54] ( Viscosity average molecular weight 21,500) 70 parts by weight, as an additive 2,
5 parts by weight of 6-bis-tert-butyl-4-methylphenol (Sumitomo Chemical Co., Ltd .: Sumilizer BHT) was mixed, and solid content was 21 wt% using tetrahydrofuran as a solvent.
The charge transport layer coating liquid of was prepared, applied on the charge generation layer, and dried at 110 ° C. for 1 hour to form a charge transport layer having a film thickness of 21 μm.

[0079]

[Chemical 34]

Example 2 8 parts by weight of a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 42] was used as a binder resin for the charge transport layer in Example 1.
A sample was prepared in the same manner as in Example 1 except that the polycarbonate resin having the repeating unit represented by the structural formula [Chemical Formula 59] was used in an amount of 72 parts by weight. (Example 3) In Example 1, 72 parts by weight of a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 42] was used as a binder resin for the charge transport layer, and a repeating unit represented by a structural formula [Chemical Formula 59] was included. A sample was prepared in the same manner as in Example 1 except that the polycarbonate resin was 8 parts by weight.

Example 4 A sample was prepared in the same manner as in Example 1 except that the styryl compound represented by the structural formula [Chemical Formula 27] was used as the charge transport material for the charge transport layer in Example 1. . (Example 5) A sample was prepared in the same manner as in Example 1 except that the amine compound represented by the structural formula [Chemical Formula 36] was used as the charge transporting material for the charge transporting layer.

Example 6 A sample was prepared in the same manner as in Example 1 except that the hindered amine compound represented by the structural formula [Chemical Formula 60] was used as the additive for the charge transport layer in Example 1.

[Chemical 35]

Example 7 In Example 1, 2,6-bis-tert-butyl-4 was used as an additive for the charge transport layer.
-Methylphenol (Sumitomo Chemical Co., Ltd .: Sumilizer BH
T) A sample was prepared in the same manner as in Example 1 except that 5 parts by weight and a hindered amine compound represented by the structural formula [Chemical Formula 60] was used. Example 8 The oxotitanyl phthalocyanine of the charge generation layer in Example 1 was analyzed by X-ray diffraction spectrum
The Bragg angle (2θ ± 0.2 °) shows a maximum diffraction peak at 9.4 ° and is at least 7.4 °, 9.7 °, and 2
A sample was prepared in the same manner as in Example 1 except that crystalline oxotitanyl phthalocyanine showing a diffraction peak at 7.3 ° was used.

Comparative Example 1 Only 150 parts by weight of a polycarbonate resin (viscosity average molecular weight 50,000) having a repeating unit represented by the structural formula [Chemical Formula 42] was used as the binder resin for the charge transport layer in Example 1. A sample was prepared in the same manner as in Example 1. (Comparative Example 2) In Example 1, as a binder resin for the charge transport layer, a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 59] (viscosity average molecular weight 40,0) was used.
00) A sample was prepared in the same manner as in Example 1 except that only 150 parts by weight was used.

Comparative Example 3 Only 150 parts by weight of a polycarbonate resin (viscosity average molecular weight 21,500) having a repeating unit represented by the structural formula [Chemical Formula 54] was used as the binder resin for the charge transport layer in Example 1. A sample was prepared in the same manner as in Example 1. (Comparative Example 4) In Example 1, a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 42] as a binder resin for the charge transport layer (viscosity average molecular weight 50,0
00) 75 parts by weight and a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 59] (viscosity average molecular weight 4
A sample was prepared in the same manner as in Example 1 except that the amount was set to 75 parts by weight.

(Comparative Example 5) In Example 1, 75 parts by weight of a polycarbonate resin (viscosity average molecular weight 40,000) having a repeating unit represented by the structural formula [Chemical Formula 59] was used as the binder resin for the charge transport layer and the structural formula [ A sample was prepared in the same manner as in Example 1 except that 75 parts by weight of a polycarbonate resin (viscosity average molecular weight 21,500) having a repeating unit represented by Chemical formula 45] was used.

Comparative Example 6 75 parts by weight of a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 42] (viscosity average molecular weight 50,000) as the binder resin for the charge transport layer in Example 1 and the structural formula [ A sample was prepared in the same manner as in Example 1 except that 75 parts by weight of a polycarbonate resin (viscosity average molecular weight 21,500) having a repeating unit represented by Chemical formula 54] was used.

Comparative Example 7 In Example 1, 30 parts by weight of a polycarbonate resin having a repeating unit represented by the structural formula [Chemical Formula 42] (viscosity average molecular weight 50,000) was used as the binder resin for the charge transport layer and the structural formula [ [Chemical Formula 59] 30 parts by weight of a polycarbonate resin (viscosity average molecular weight 40,000) having a repeating unit represented by the chemical formula [Chemical Formula 5]
4] A sample was prepared in the same manner as in Example 1 except that 90 parts by weight of a polycarbonate resin (viscosity average molecular weight 21,500) having a repeating unit represented by [4] was used.

(Comparative Example 8) A sample was prepared in the same manner as in Example 1 except that the additive for the charge transport layer was omitted. (Comparative Example 9) In Comparative Example 9, except that 4-dibenzylamino-2-methylbenzaldehyde-1,1-diphenylhydrazone (CTC-191 manufactured by Takasago Chemical Co., Ltd.) was used as the charge transport material for the charge transport layer in Example 1. A sample was prepared in the same manner as in Example 1.

(Evaluation)Initial image evaluation Prototype on a commercial copying machine (Sharp: AR-450)
Equipped with an electrophotographic photoconductor to check halftone images
It wasEvaluation of electric potential Next, take out the developing tank and replace it with the surface potential at the development site.
Set the total (Made by Trek: Model 344), black
Potential VO of solid original, potential VH of halftone original, white
The potential VL of the solid original was measured.

[0091]Durability evaluation Remove the surface electrometer and mount the developing tank on the evaluation copier again.
After loading, A4: After copying 30,000 sheets, same as the initial
Was measured and the change during repeated use was evaluated. Well
The cleaning blade friction noise was also evaluated at the same time. Criticism
The value results are shown in Table 1.

[0092]

[Table 1]

In the examples in which the three kinds of resins of the present invention were combined, all of the image characteristics, electrical characteristics, wear resistance and friction noise were good, but as in Comparative Examples 1, 3, and 6, the general formula was used. When the polycarbonate resin composed of the repeating units of [2] and [3] was not used, friction noise with the cleaning blade was generated. Further, as in Comparative Examples 2, 3 and 5, when the polycarbonate resin composed of the repeating unit of the structural formula [1] was not used, the wear amount was increased. Further, as in Comparative Examples 1, 2 and 4, when the polycarbonate resin composed of the repeating unit of the structural formula [4] was not used, unevenness occurred in the drum cycle after 30,000 sheets were used. As a result, the periodic unevenness occurs even when no phenol-based or amine-based additive is used in the charge transport layer as in Comparative Example 8. Further, in Comparative Example 9 using a material other than the preferred charge transport material, the image density was low and the result was not suitable for a high speed process because of poor sensitivity.

[0094]

As is clear from the above examples and comparative examples, according to the present invention, an electrophotographic photoreceptor having mechanically high durability is obtained. Further, it becomes an electrophotographic photoreceptor having high durability electrically and chemically. Further, according to the present invention, a highly sensitive and highly durable electrophotographic photosensitive member can be obtained, and further,
An electrophotographic photoreceptor having excellent chemical stability and durability can be obtained.

[Brief description of drawings]

FIG. 1 is a view showing a laminated photoreceptor in which a charge generation layer and a charge transport layer are laminated on a conductive support.

FIG. 2 is a view showing a laminated type photoreceptor in which a charge transporting layer and a charge transporting layer are laminated in reverse on a conductive support.

FIG. 3 is a diagram showing a laminated type photoreceptor including three layers of an intermediate layer, a charge generation layer, and a charge transport layer.

FIG. 4 is a diagram showing a photoreceptor including an intermediate layer and a photosensitive layer.

[Explanation of symbols]

1 Conductive support 2 Charge generation material 3 Charge transport materials 4 Photosensitive layer 5 Charge generation layer 6 Charge transport layer 7 Surface protection layer 8 Middle layer (undercoat layer)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) G03G 5/06 371 G03G 5/06 371 (72) Inventor Rikiya Matsuo 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka No. Sharp Co., Ltd. (72) Inventor Sayaka Fujita 22-22 Nagaike-cho, Abeno-ku, Osaka-shi, Osaka Inside Sharp Co., Ltd. (72) Takahiro Teramoto No. 22-22 Nagaike-cho, Abeno-ku, Osaka-shi, Osaka In-house F-term (reference) 2H068 AA13 AA16 AA19 AA20 BA12 BA13 BA14 BA39 BA60 BB25 BB32 BB54

Claims (8)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer containing at least a charge generating material, a charge transporting material and a binder resin on a conductive substrate, wherein the photosensitive layer is represented by the following general formula [1] as a binder resin. A polymer having a structural unit represented by the following general formula [2] and a polymer having a repeating unit represented by the following general formula [3] and a structural unit represented by the following general formula [4] as a main component An electrophotographic photosensitive member comprising a polymer of [Chemical 1] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a carbon atom. Represents a cyclic hydrocarbon residue of the formulas 4 to 10, a substituted or unsubstituted aryl group, and L is an integer. (In the formula, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ¹ is each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and each X independently represents an alkylene group having 2 or more carbon atoms or an alkyleneoxy group having 2 or more carbon atoms. Is an alkylene group,
X ′ is independently an alkylene group having 2 or more carbon atoms, an alkyleneoxyalkylene group having 2 or more carbon atoms, or an oxygen atom, a is each independently an integer of 0 to 4, and na is 0 or 1. nb is 1 or 2, nc is 1 or 2, provided that na + nb + nc = 3, n1, n
2, n3 and n4 are each independently an integer of 0 or 1 or more, provided that n1 + n2 + n3 + n4 = 0 to 450. ) [Chemical 3] (In the formula, each R ² is independently a halogen atom, a vinyl group, an allyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and 3 carbon atoms. To a substituted or unsubstituted cycloalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, and a is independently 0 to Is an integer of 4,
Y is a single bond, -O-, -CO-, -S-, -SO-,-.
_{^{SO 2 -, - CR 3 R}} 4 -, a substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms, a substituted or unsubstituted 2 to 12 carbon atoms alpha, .omega. alkylene group, 9,9
Fluorenylidene group, 1,8-menthanediyl group, 2,
8-menthanediyl group, a substituted or unsubstituted pyrazilidene group or a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, provided that R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C 1 to 10 carbon atom or It is an unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ) [Chemical 4] (In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R
¹⁴ , R ¹⁵ and R ¹⁶ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon residue having 4 to 10 carbon atoms, a substituted or unsubstituted aryl group. . Z is a group of atoms necessary for forming a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocycle. m is an integer. ) 2. A mixture of a polymer having a structural unit represented by the general formula [1] as a main component and a polymer including repeating units represented by the general formula [2] and the general formula [3]. The electrophotographic photosensitive member according to claim 1, wherein the weight ratio is 1: 9 to 9: 1. 3. The electrophotography according to claim 1, wherein the polymer resin containing the structural unit represented by the general formula [4] as a main component is contained in a proportion of less than 50% by weight. Photoconductor. 4. The charge transporting material is a charge transporting material represented by the following general formula [5].
The electrophotographic photosensitive member according to any one of 3 above. [Chemical 5] [In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each represent an aryl group which may have a substituent, and Ar _{1 to} Ar _1
At least one of ₄ is an aryl group having a substituted amino group as a substituent. n represents 0 or 1. ] 5. The charge transporting material is a charge transporting material represented by the following general formula [6].
The electrophotographic photosensitive member according to any one of 3 above. [Chemical 6] [In the formula, Ar ₅ represents an aryl group which may have a substituent, Ar ₆ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent, and R ₁₇ represents hydrogen. Represents an atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent,
Y represents an aryl group or the like which may have a substituent. ] 6. The charge transporting material is a charge transporting material represented by the following general formula [7].
The electrophotographic photosensitive member according to any one of 3 above. [Chemical 7] [In formula, R < ₁₈ > -R < ₂₃ > is a hydrogen atom, a halogen atom,
Alkyl group or alkoxy group, r and s are 1 to 4, p,
q, t, and u represent the integer of 1-5. ] 7. The charge generation material exhibits a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.4 ° in an X-ray diffraction spectrum, and at least 7.4 ° and 9.
7. The electrophotographic photoconductor according to claim 1, wherein crystalline oxotitanyl phthalocyanine having a diffraction peak at 7 ° and 27.3 ° is used. 8. The charge transporting layer or both the charge transporting layer and the charge generating layer contain a phenol-based and / or amine-based antioxidant, according to any one of claims 1 to 7. Electrophotographic photoreceptor.