WO2006003897A1 - Electrophotographic photoreceptor - Google Patents

Abstract

This invention provides an electrophotographic photoreceptor, suitable for use in contact electrification devices, which does not suffer from drawbacks involved in conventional electrophotographic photoreceptors and can withstand printing of a large number of sheets by virtue of reduced abrasion loss and surface roughness of a photosensitive layer in the electrophotographic photoreceptor. The electrophotographic photoreceptor includes a photosensitive layer provided on an electrically conductive support. The photosensitive layer comprises at least a charge generating agent, a charge transfer agent, and a binder resin. In the photosensitive layer, the binder resin comprises a polycarbonate copolymer comprising repeating units represented by the first following formula, and the charge transfer agent comprises a compound represented by the second following formula.

Description

 Specification

 Electrophotographic photoreceptor

 Technical field

 [0001] The present invention relates to an electrophotographic photosensitive member used in an electrophotographic apparatus such as a copying machine or a laser beam printer.

 Background art

 In recent years, a phthalocyanine cyanide compound known as an organic photoconductive material as an electrophotographic photosensitive member is used as a charge generation layer, and a charge transfer layer having a hydrazone compound is also laminated. Function-separated organic photoconductors have become mainstream.

 [0003] As the binder resin used in this organic photoreceptor, bisphenol A type polycarbonate resin has been most commonly used. However, when the photosensitive layer is formed using bisphenol A type polycarbonate resin as the binding resin, there are disadvantages such as the coating solution of the photosensitive layer being unstable.

 [0004] In addition, since the photosensitive layer using this binding resin has a large coefficient of friction on the surface, when the electrophotographic photosensitive member is mounted on an electrophotographic apparatus and the electrophotographic process is repeated, the surface of the photosensitive layer is removed. The cleaning blade, which is generally used for cleaning the residual toner, turned over and some troubles occurred, such as generating abnormal noise.

 [0005] Furthermore, since this polycarbonate resin has poor oil resistance, it may accidentally touch the surface of the photosensitive layer during maintenance of the electrophotographic apparatus, and fingerprints may be attached. In some cases, cracks occurred in the parts with fingerprints, making the electrophotographic photoreceptor unusable.

 On the other hand, in consideration of the stability of the coating solution, it has also been proposed to use bisphenol Z-type polycarbonate resin as the material of the photosensitive layer of the electrophotographic photosensitive member. However, using this bisphenol Z-type polycarbonate resin did not solve the problem of blade reversal or abnormal noise or cracking.

[0007] Thereafter, a polycarbonate copolymer having a siloxane structure was developed, and a polycarbonate copolymer used in combination with a charge transfer agent was also proposed (for example, see Patent Document 1). Patent Document 1: Japanese Unexamined Patent Publication No. 2000-169309

However, this also proved that the above problems could not be solved completely.

[0009] Furthermore, in the charging process in the electrophotographic apparatus, the force that has been generally applied to the surface of the photoreceptor by corona charging is less ozone generation than corona charging. A charging member called contact charging is directly applied to the charging member. The method of applying a charge by contacting the photoconductor is becoming mainstream. Although this method has an ozone suppression effect, since the charging member and the photosensitive member are in direct contact with each other, there is a problem such as a relatively large amount of film scraping on the surface layer of the photosensitive member or a decrease in charging potential due to a decrease in film thickness. Invite them to take countermeasures. Along with the increase in process speed, the reduction of the photosensitive layer due to process running has also become an issue. When the amount of film reduction increases, the density of the printed image decreases and positive memory is generated.

 [0010] In addition, toner filming, which appears to be caused by the surface roughness of the photosensitive layer, often produces black stripes due to paper powder.

 Disclosure of the invention

 Problems to be solved by the invention

An object of the present invention is to reduce the amount of wear and surface roughness of a photosensitive layer of an electrophotographic photosensitive member used in an electrophotographic apparatus, thereby enabling printing of a large number of sheets without the disadvantages found in conventional ones. It is an object to provide an electrophotographic photoreceptor that can withstand.

 Means for solving the problem

 [0012] As a result of intensive studies to solve the above problems, the present inventors have found that a charge transfer agent having a specific structure containing a polycarbonate copolymer having a specific structure as a binding resin in the photosensitive layer. The electrophotographic photoreceptor used has been found to maintain the excellent electrostatic characteristics over a long period of time without the problems of the prior art, and the present invention has been completed.

That is, according to the photoreceptor using the specific polycarbonate copolymer resin represented by the general formula (1) to be described later, the change in the friction coefficient of the photoreceptor surface due to continuous printing is reduced as compared with the conventional case. It was found that an electrophotographic photosensitive member that can withstand printing on a large number of sheets can be provided. Furthermore, the molecular weight of the main chain polycarbonate copolymer resin is 1,000 -100, If the range of 000 is preferred, exceeding 100,000, the viscosity becomes too high and the film formability is difficult. Further, it has been proved that the combination with the charge transfer agent represented by the general formula (2), which will be described later, improves the compatibility and wear resistance, and provides a photoreceptor that provides excellent electrophotographic characteristics.

 [0014] The invention according to claim 1, which has been made on the basis of a strong viewpoint, is an electrophotographic photosensitive member in which a photosensitive layer having at least a charge generating agent, a charge transfer agent, and a binder resin is formed on a conductive support. And a polycarbonate copolymer containing a repeating unit represented by the general formula (1) as a binder resin in the photosensitive layer, and a compound represented by the general formula (2) as a charge transfer agent. An electrophotographic photosensitive member characterized by the following.

 [0015] General formula (1)

 [Chemical 1]

 [Wherein R and R are each independently a hydrogen atom, halogen atom, trifluoromethyl group, carbon

 1 2

 Any of a prime alkyl group having 1 to 12 or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms A is an integer of 1 to 200, X is —O—, or the following general formula (3) or (3 ′) (wherein R is a hydrogen atom, a halogen atom, trifluoromethyl, Base

 Three

 , An alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms And b and b ′ are each independently an integer of 0 to 6, and c is an integer of 0 to 4. X represents —O—, or the following general formula (4) or (4 ′) (

 2

 In the formula, R represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms.

Four

 Or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms. ), And f and f are each independently an integer of 0 to 6, and 1 is an integer of 0 to 4. ]

一般式 (3' ) General formula (3) [Chemical 2]

General formula (3 ')

[Chemical formula 3] NH—— (CH ₂ ) _b , general formula (4)

一般式 (4' ) [Chemical 4]

General formula (4 ')

[Chemical 5]

—— (CH ₂ ) _f —— NH — General formula (2)

[Chemical 6]

[In the formula, R to R are each independently hydrogen, halogen atom, or optionally substituted carbon atoms 1 to

 5 9

6 represents an alkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and d represents an integer of 0 or 1. ] [0017] According to the invention of claim 1, which has a powerful structure, the releasability and lubricity are improved, so that the coefficient of friction of the photosensitive layer is reduced.

 Further, by containing the compound represented by the general formula (2) as a charge transfer agent, a photoreceptor having little compatibility and environment dependency can be provided.

[0018] The invention according to claim 2 is an electrophotographic photosensitive member characterized by containing a polycarbonate copolymer containing a repeating unit represented by the general formula (5).

[0019] General formula (5)

 [Chemical 7]

— 0— R ₃ — (CF ^ _e — R32

[Wherein R is a halogen atom, an alkylene group, an arylene group having 6 to 12 carbon atoms, or a substituent.

 31

 Any one of the arylene groups, R represents a hydrogen atom or a fluorinated alkyl group, and e represents

 32

 , Represents an integer of 1-20. ]

[0020] According to the invention of claim 2, having a powerful structure, the combination of the general formula (1) and the general formula (5) with the specific structural group further improves the releasability and lubricity, The friction coefficient of the layer can be reduced.

[0021] The invention according to claim 3 is an electrophotographic photosensitive member characterized by containing a polycarbonate copolymer containing a repeating unit represented by the general formula (6).

[0022] General formula (6)

 [Chemical 8]

[In the formula, R to R each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number.

 33 36

 It represents any of 6 to 12 aryl groups or substituted aryl groups, and g, h and i each independently represent an integer of 0 to 4. ]

According to the invention described in claim 3 having a powerful configuration, the general formula (1) and the general formula (6) The combination with the specific structural group improves the compatibility and has the effect of improving the film formability.

 [0024] The invention according to claim 4 is an electrophotographic photosensitive member comprising a polycarbonate copolymer having a structure represented by the general formula (7).

 General formula (7)

 [Chemical 9]

(Wherein R and R are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, carbon

 37 38

 It represents either an aryl group or a substituted aryl group of formulas 6 to 12, and m independently represents an integer of 0 to 4. j and k are the straight chain numbers of saturated hydrocarbons and are integers of 1-20. [0025] According to the invention of claim 4, having a powerful structure, the combination with the specific structural group of the general formula (1) and the general formula (7) improves the compatibility and improves the film formability. Has the effect of

 [0026] The invention according to claim 5 is an electrophotographic photosensitive member comprising a polycarbonate copolymer having a structure represented by the general formula (8).

 General formula (8)

 [Chemical 10]

〔式中、 R 〜R は、各々独立にハロゲン原子、炭素数 1〜12のアルキル基、シクロ

[Wherein R 1 to R 4 are each independently a halogen atom, an alkyl group having 1 to 12 carbon atoms,

39 42

 Represents a hexyl group, an aryl group having 6 to 12 carbon atoms, or a substituted aryl group, and B represents a single bond, —O—, —CO—, —S—, —SO—, or —SO—. P, q, r

 2

 And s is an integer from 0 to 4. ]

[0027] According to the invention of claim 5 having a powerful configuration, the combination of the general formula (1) and the general formula (8) with the specific structural group further improves the releasability and lubricity, The friction coefficient of the layer can be reduced.

[0028] The invention according to claim 6 is an electrophotographic photosensitive member comprising a charge transfer agent having a structure represented by the general formula (9).

 General formula (9)

 [Chemical 11]

[Wherein R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms which may have a substituent.

 10 11

 R 1 represents either a hydrogen atom or a dialkylamino group. ]

 12

 [0029] According to the invention of claim 6, having a powerful structure, the combination of the general formula (1) and the general formula (9) with the specific structural group further improves the releasability and lubricity, and the photosensitive property. The friction coefficient of the layer can be reduced.

[0030] The invention according to claim 7 is an electrophotographic photosensitive member comprising a charge transfer agent having a structure represented by the general formula (10).

 General formula (10)

[Chemical 12]

[Wherein R to R each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.

 13 16

 And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ]

[0031] According to the invention of claim 7, having a powerful structure, the combination of the general formula (1) and the general formula (10) with the specific structural group further improves the releasability and lubricity, The friction coefficient of the layer can be reduced.

[0032] The invention according to claim 8 is an electrophotographic photosensitive member comprising a charge transfer agent having a structure represented by the general formula (11).

 General formula (11)

 [Chemical 13]

[In the formula, R 1 to R 4 each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms.

 17 20

 And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ]

[0033] According to the invention of claim 8, having a powerful structure, the combination of the general formula (1) and the general formula (11) with the specific structural group further improves the releasability and lubricity, The friction coefficient of the layer can be reduced.

[0034] The invention according to claim 9 is an electrophotographic photosensitive member comprising a charge transfer agent having a structure represented by the general formula (12). General formula (12)

[Chemical 14]

 [Wherein, R represents ~ R each independently represents a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms.

 21 24

It represents the difference between aryl group, alkoxy group, or aryl group.

, R is a hydrogen atom, a halogen atom, an alkyl or alkoxy group having 1 to 6 carbon atoms,

twenty five

It represents either a aryl group having a substituent, a hydrocarbon group or an alkadienyl group having a substituent, or a general formula (12 ′), and t is 0 or 1 Represents an integer. ]

General formula (12 ')

[Chemical 15]

(In the formula, R and R are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.

 26 27

Or an aryl group, or an aryl group, and w represents an integer of 0 or 1. )

 According to the invention of claim 9, which has a powerful structure, the combination of the general structural formulas (1) and (12) with the specific structural group further improves the photoresponsiveness and increases the sensitivity of the photoreceptor. Can be realized.

The invention according to claim 10 contains a charge transfer agent having a structure represented by the general formula (13) The electrophotographic photosensitive member according to claim 1, wherein c is

 General formula (13)

 [Chemical 16]

力かる構成を有する請求項 10記載の発明によると、一般式（1)及び一般式（ 13)と の特定構造基との組み合わせにより、光応答性を一層向上させ、感光体の高感度化 を実現することができる。

According to the invention of claim 10 having a powerful configuration, the combination of the general structural formula (1) and the general structural formula (13) with the specific structural group can further improve the photoresponsiveness and increase the sensitivity of the photoreceptor. Can be realized.

[0036] The binder resin used in the photosensitive layer of the present invention is represented by the following general formula (1), general formula (3), general formula (4), general formula (5), general formula (6), Specific examples of general formula (7) and general formula (8) are shown below.

However, it is not limited to these.

A specific example of the general formula (1) is shown below.

 Formula (la)

 [Chemical 17]

式 (lc) [化 19]

式（Id)

Formula (lc) [Chemical 19]

Formula (Id)

[Chemical 20]

[0038] A specific example of the general formula (5) is shown below.

 Formula (5a)

 [Chemical 21]

—0— CH ₂ ""-(CF ^) —— H

[0039] Formula (5b)

— ^Cp3 [Chemical 22]

— ^Cp 3

[0040]

[Chemical 23]

[0041] Formula (5d)

[0042] 一般式 (6)の具体例を以下に示す, 式（6a) [Chemical 24]

[0042] A specific example of the general formula (6) is shown below.

[Chemical 25]

 Formula (6b)

[Chemical 26]

 [0044] Formula (6c)

[Chemical 27]

CH ₃

 [0045] Formula (6d)

 [Chemical 28]

 H

[0046] Formula (6e)

[Chemical 29]

 [0048] A specific example of the general formula (7) is shown below.

 Formula (7a)

 [Chemical 31]

 [0050] Specific examples of the general formula (8) are shown below.

 Formula (8a)

[Chemical 33]

[0051] Hereinafter, the charge transfer agent used in the photosensitive layer of the present invention is not limited to these forces showing specific examples of the general formula (9).

[0052] Formula (9a)

 [Chemical 34]

[0053] Formula (9b)

 [Chemical 35]

[0054] Formula (9c)

[Chemical 36]

[0055] Specific examples of the general formula (10) are shown below.

 Formula (10a)

 [Chemical 37]

A specific example of the general formula (11) is shown below.

[0057] Formula (11a)

 [Chemical 38]

[0058] Formula (l ib)

[Chemical 39]

式（12b)

Formula (12b)

式（12c) [Chemical 42]

Formula (12c)

[Chemical 43]

式（12d)

Formula (12d)

[Chemical 44]

一般式（13)の具体例を以下に示す。 式（13a)

Specific examples of general formula (13) are shown below. Formula (13a)

[Chemical 45]

Formula (13b)

 [Chem 46]

Effect of OCH ₃ invention

 [0064] The electrophotographic photosensitive member of the present invention is not affected by electrostatic characteristics such as surface potential and sensitivity, and the amount of film loss after printing is very small and the surface roughness is small. Molly, toner filming and black streaks are not generated at all.

 Therefore, according to the present invention, an electrophotographic photosensitive member having excellent electrophotographic characteristics and having a long life can be provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0065] Hereinafter, preferred embodiments of the electrophotographic photoreceptor according to the present invention will be described in detail.

The present invention provides, for example, a charge containing at least a charge generating agent on a conductive support. The present invention is applied to a function-separated electrophotographic photoreceptor in which a generation layer is formed and a charge transfer layer containing at least a charge transfer agent is formed thereon. In this case, a photosensitive layer is formed by the charge generation layer and the charge transfer layer.

 The present invention also relates to a single-layer electrophotographic photosensitive member in which a charge generating agent and a charge transfer agent are contained in the same layer, or an inversely laminated electrophotographic photosensitive member in which a charge transferring layer and a charge generating layer are laminated in this order. It can be applied to the above.

 [0066] Examples of the conductive support that can be used in the present invention include aluminum, brass, stainless steel, nickel, chromium, titanium, gold, silver, copper, tin, platinum, molybdenum, indium, and the like, and simple substances and alloys thereof Processed materials and conductive materials such as the above metals and carbon by vapor deposition, plating, etc., and made conductive plastic plates and films, and also with acid tin, oxide oxide, aluminum iodide. The conductive support can be formed using various materials having conductivity that are not limited to the type and shape, such as coated conductive glass. As for the shape of the conductive support, a drum shape, a rod shape, a plate shape, a sheet shape, or a belt shape can be used.

[0067] In general, a cylindrical aluminum tube alone or a surface thereof anodized, or an aluminum tube or an alumite layer formed with a resin layer is often used. This resin layer has a function of improving adhesion, a barrier function for preventing an inflow current of the support, and a defect covering function for the support surface. This resin layer consists of polyethylene resin, acrylic resin, epoxy resin, polycarbonate resin, polyurethane resin, chlorinated resin, acetic acid resin, polyvinyl butyral resin, polyamide resin, nylon resin Various types of fats such as fat can be used. These resin layers may be composed of a single resin, or two or more kinds of resin may be mixed, or may be combined with an alumite treatment. In addition, metal compounds, metal oxides, carbon, silica, resin powder, etc. can be dispersed in the layer. Furthermore, various pigments, electron-accepting substances, electron-donating substances, etc. are included for improving the characteristics.

[0068] As the charge generating agent that can be used in the present invention, disazo pigments and oxytitanium phthalocyanine are desirable in terms of compatibility of sensitivity, but are not limited thereto. Others such as selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, Metal phthalocyanine, other metal phthalocyanine pigments, monoazo pigments, trisazo pigments, polyazo pigments, indigo pigments, selenium pigments, toluidine pigments, pyrazoline pigments, perylene pigments, quinacridone pigments, polycyclic quinone pigments, pyrylium salts, etc. can be used. .

 [0069] These charge generating agents may be used alone, or two or more of them may be used in combination to obtain a sensitizing action with an appropriate photosensitivity wavelength.

In the electrophotographic photoreceptor of the present invention, oxytitanium phthalocyanine is particularly suitable as a charge generator.

 [0071] Further, the polycarbonate copolymer of the present invention has a reduced viscosity (7? / C) at 20 ° C of a solution of 0.5 g Zdl in methylene chloride as a solvent and not less than 0.46 dlZg. Membrane

 sp

 This is preferable because the hardness of the photosensitive layer is increased.

 Furthermore, the molecular weight 【Ma, especially in the range of 20, 000 to 70, 000 force! / ,.

 Further, the copolymerization ratio of the polycarbonate resin structure represented by the general formula (1) is 0.02 to: L 0

The range is Omol%, preferably 0.1 to 0.5 mol%.

[0072] In addition, when the photosensitive layer has a laminated type or a reverse laminated type, the binder resin of the present invention may be used for one or both of the charge generation layer and the charge transfer layer. In view of its characteristics, the resin is preferably contained when it is contained in the outermost surface layer, since the desired characteristics are sufficiently exhibited.

 [0073] On the other hand, in the electrophotographic photoreceptor of the present invention, a binder resin other than the above-mentioned specific polycarbonate-copolymer can be contained in the photosensitive layer.

[0074] As the binder resin that can be used to form the photosensitive layer, thermoplastic resin, thermosetting resin, photocurable resin, and the like can be used. These resins include polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene monoacetate resin, polypropylene resin, chlorinated resin, chlorinated polyether, Butyl chloride Acetic acid resin, polyester resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin, epoxy resin, polyarylate resin Resin, diarylate resin, polysulfone resin, polyethersulfone resin, polyallylsulfone resin, silicone resin, ketone resin, polyvinylino butylene resin resin, polyether resin, phenol resin, EVA (ethylene 'Vinyl acetate' copolymer) There are resin, ACS (acrylonitrile 'chlorinated polyethylene' styrene) resin, ABS (atari mouth-tolyl 'butadiene' styrene) resin, epoxy acrylate, etc. These can be used alone or in combination of two or more. It is also possible to use a mixture of rosin having different molecular weights.

If V, hardness is better because it can improve wear resistance.

The electrophotographic photoreceptor of the present invention contains at least one compound represented by the general formula (2) as a charge transfer agent in the photosensitive layer.

In this case, the content of the compound represented by the general formula (2) in the charge transfer layer is preferably 0.3 to 2.0 parts by weight with respect to 1 part by weight of the binder resin. More preferably, it is 0.5 to 1.2 parts by weight.

 [0077] If the content of this compound is less than 0.3 parts by weight, the electrical characteristics such as the increase in residual potential are deteriorated. On the other hand, when the amount is more than 2.0 parts by weight, mechanical properties such as wear resistance are deteriorated.

 Of the compounds represented by the general formula (2), the compounds represented by the general formulas (9), (10), (11), and (12) are particularly preferable.

 Of the compounds represented by the general formula (2), those having an IP value of 4.95 to 5.25 eV are particularly preferable.

 [0079] Further, another charge transfer agent may be added to the photosensitive layer of the electrophotographic photoreceptor of the present invention. In that case, since the sensitivity of the photosensitive layer can be increased and the residual potential can be lowered, the characteristics of the electrophotographic photosensitive member of the present invention can be improved.

 [0080] Examples of the charge transfer agent that can be added to improve the properties include polyvinyl carbazole, halogenated polybulcarbazole, polyburpyrene, polybulindoloquinoxaline, polybulubenzothiophene, polybulu. Anthracene, Polybulatridine, Polyburpyrazoline, Polyacetylene, Polythiophene, Polypyrrole, Polyphenylene, Polyphenylenevinylene, Polyisothianaphthene, Polyaniline, Polydiacetylene, Polyheptadien, Polypyridinediyl, Polyquinoline, Polyphenol Conductive polymer compounds such as rensulfide, polyferroceylene, polyperinaphthylene, and polyphthalocyanine can be used.

[0081] Further, as low molecular weight compounds, tri-trofluorenone, tetracyanethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof Body, polycyclic aromatic compounds such as anthracene, pyrene, phenanthrene, nitrogen-containing heterocyclic compounds such as indole, carbazole, imidazole, fluorenone, fluorene, oxadiazole, oxazole, pyrazoline, triphenylmethane, enamine, stilbene, Tagen, hydrazone, triphenylamine compounds other than those mentioned above, and the like can be added as charge transfer agents.

 [0082] Also, as a charge transfer agent for the same purpose, a polymer solid obtained by doping a polymer compound such as polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethacrylic acid or the like with a metal ion such as Li (lithium) ion. An electrolyte or the like can also be added.

 [0083] Further, as a charge transfer agent for the same purpose, an organic charge transfer complex formed of an electron donating substance typified by tetrathiafulvalene-tetracyanoquinodimethane and an electron accepting substance can be used. Can do.

 The charge transfer agent can obtain desired photoreceptor characteristics even when only one kind is added or when two or more kinds of compounds are mixed and added.

 [0084] The electrophotographic photosensitive member of the present invention contains an antioxidant or an ultraviolet ray in the photosensitive layer for the purpose of property change due to oxidative deterioration of the photoconductive material or binder resin, prevention of cracks, and improvement of mechanical strength. It is preferred to contain an absorbent.

[0085] Antioxidants that can be used in the present invention include 2,6-di-tert-butylphenol, 2,6-ditert-4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, 2,4 dimethylol. 6 tert butylphenol, 2, 6 di-tert-butyl-4 methylphenol, butylated hydroxysol, stearyl propionate 13 (3,5-ditert-butyl 4-hydroxyphenol), α-tocopherol, j8-tocopherol, n-octadecyl 3- (3, -5, -di-tert-butyl-4, -hydroxyphenol) propionate and other monophenols, 2,2, -methylenebis (6-tert-butyl 4-methyl) Phenol), 4, 4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4, 4, -thiobis (6-tert-butyl-3-methylphenol), 1, 1, 3 Lis (2-methyl-4-hydroxy-5-tert-butylphenol) butane, 1, 3, 5-trimethyl-2,4,6 tris (3,5 ditert-butyl-4-hydroxybenzyl) benzene, tetrakis [ Methylene 3 (3,5-di-tert-butyl-4-hydroxyphenol) Mouth Pionate] Polyphenols such as methane are preferred, and one or more of them can be simultaneously contained in the photosensitive layer.

 [0086] Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenol) benzotriazole, 2- [2-hydroxy-3,5-bis (α, a-dimethylbenzyl) phenol] 2 H benzo Triazole, 2— (3,5 di-tert-butyl 2-hydroxyphenol) benzotriazole, 2 -— (3-tert-butyl-5-methyl-2-hydroxyphenol) -5 —clobenzotriazole, 2-— (3,5-Di-tert-butyl-2-hydroxyphenol) —5 Chronobenzotriazole, 2-— (3,5 Di-tert-amylu 2 hydroxyphenyl) benzotriazole, 2- (2 , -Hydroxy-5,1 tert-octylphenol) benzotriazoles such as benzotriazole, salicylic acid phenol, salicylic acid p-tert-butylphenol, salicylic acid p-octylphenol etc. are preferred. One or more of them can be simultaneously contained in the photosensitive layer.

 [0087] In addition, the anti-oxidation agent and the ultraviolet absorber can be added simultaneously. These added calories may be any layer in the photosensitive layer, but are preferably added to the outermost layer, particularly the charge transfer layer.

 [0088] The addition amount of the antioxidant is preferably 3 to 20% by weight with respect to the binder resin, and the addition amount of the ultraviolet absorber is 3 to 30 with respect to the binder resin. It is preferable to set it as weight%.

. Furthermore, when both an acid proof agent and an ultraviolet absorber are added, the amount of added calories of both components is preferably 5 to 40% by weight with respect to the binder resin.

[0089] In addition to the antioxidant and the ultraviolet absorber, a light stabilizer such as a hindered amine or a hindered phenol compound, an anti-aging agent such as a diphenylamine compound, a surfactant or the like may be added to the photosensitive layer. You can also.

[0090] As a method for forming a photosensitive layer, a method is generally used in which a coating solution is prepared by dispersing or dissolving in a solvent together with a predetermined photosensitive material and a binder resin, and coating on a predetermined surface. is there.

[0091] As the coating method, dip coating, curtain flow, bar coating, roll coating, ring coating, spin coating, spray coating, etc. can be performed according to the shape of the base and the state of the coating liquid. Monkey.

The charge generation layer can also be formed by a vacuum deposition method. [0092] Solvents used in the coating liquid include alcohols such as methanol, ethanol, n-propanol, i-propanol and butanol, pentane, hexane, heptane, octane, cyclohexane and cycloheptane. Saturated aliphatic hydrocarbons, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as dichloromethane, dichloroethane, black mouth form, black mouth benzene, dimethyl ether, jetyl ether, tetrahydrofuran (THF), methoxyethanol, etc. Ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, N, N dimethylformamide, dimethylsulfoxy There are These can be used alone or as a mixture of two or more solvents.

 [0093] In addition, on the surface of the photosensitive layer, organic thin films such as polyvinyl formal resin, polycarbonate resin, fluorine resin, polyurethane resin, and silicon resin, and hydrolyzed products of silane coupling agents are used. A surface protective layer may be provided by forming a thin film made of a siloxane structure body formed in (4). In this case, the durability of the photoreceptor is improved, which is preferable. This surface protective layer may be provided to improve other functions besides improving durability.

 Example

 Hereinafter, examples of the electrophotographic photosensitive member according to the present invention will be described in detail together with comparative examples.

[0095] Example 1

 A charge generation layer was formed on a cylindrical drum having a 30 mm diameter aluminum force by applying a dispersion of γ-type oxytitanium phthalocyanine using polybutyl butyral as a binder resin by dip coating.

 [0096] Next, as the binding resin, the formula (la), the formula (6b), and the formula (8a) are converted into a molar ratio (mol%) of 0.13: 49.87: 50, and the viscosity average molecular weight (Mv; 30,000 ) Polycarbonate Z siloxane copolymer (reduced viscosity 0.70 r? SpZc), a compound represented by formula (9b) as a charge transfer agent, and 2, 6 g tert-butyl 4- Methylphenol was dissolved in black mouth form at a weight ratio of polycarbonate copolymer Z charge transfer agent Z antioxidant = 1.0 / 0.8.8 / 0.1 to prepare a coating solution.

[0097] Then, after applying this coating solution by dip coating, it was dried at a temperature of 100 ° C for 1 hour. A charge transfer layer having a thickness of 24 m was formed. An electrophotographic photosensitive member was produced by the method described above.

[0098] Example 2

 The polycarbonate Z siloxane copolymer of Example 1 has a viscosity average molecular weight (Mv; 70,00 0), and the molar ratio (mol%) of the polycarbonate copolymer is expressed by the formula (la), formula (6b), formula ( An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 8a) was changed to 0.15: 80: 19.85.

[0099] Example 3

 The molar ratio (mol%) of the polycarbonate copolymer of Example 1 was changed to Example 1 except that Formula (la), Formula (6b), and Formula (8a) were set to 0.25: 49.75: 50. An electrophotographic photosensitive member was produced in the same manner.

[0100] Example 4

 The molar ratio (mol%) of the polycarbonate copolymer of Example 1 was changed to Example 1 except that Formula (la), Formula (6b), and Formula (8a) were set to 0.4: 49.6: 50. An electrophotographic photoreceptor was produced in the same manner.

[0101] Example 5

 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the polycarbonate copolymer of Example 1 was changed to formula (lb), formula (6f), and formula (8a).

[0102] Example 6

 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the polycarbonate copolymer of Example 1 was changed to Formula (Ic), Formula (7a), and Formula (8a).

[0103] Example 7

 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the formula (5c) was added to the terminal group of the polycarbonate copolymer of Example 1.

[0104] Example 8

 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transfer agent formula (9b) in Example 1 was changed to the compound represented by formula (11a).

[0105] Example 9 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transfer agent formula (9b) in Example 1 was changed to the compound represented by formula (12a).

[0106] Example 10

 Electrophotography using the same method as in Example 1, except that the formula (12a) was added to the charge transfer agent formula (9b) of Example 1 and the mixing ratio was changed to formula (9b): formula (12a) = 2: 8 A photoconductor was prepared.

 Example 11

 An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the charge transfer agent formula (9b) in Example 1 was changed to the compound represented by formula (13a).

 Example 12

 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transfer agent formula (9b) in Example 1 was changed to the compound represented by formula (13b).

[0107] Comparative Example 1

 An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the polycarbonate resin of the formula (6c) alone was used instead of the polycarbonate copolymer of Example 1.

[0108] Comparative Example 2

 An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the polycarbonate resin of formula (7a) alone was used instead of the polycarbonate copolymer of Example 1.

[0109] Comparative Example 3

 An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the formula (6b), formula (8a), and molar ratio of 0.5: 0.5 were used instead of the polycarbonate copolymer of Example 1. did.

[0110] Comparative Example 4

 The same formula as in Example 1 except that the formula (6c) of the polycarbonate copolymer of Example 1 is replaced by the formula (6b), and the hydrazone compound represented by the following formula (A) is used as the charge transfer agent. An electrophotographic photosensitive member was produced by this method.

[0111] Formula (A)

[Chemical 47]

[0112] Evaluation method

 [Measurement of electrostatic characteristics]

 Using an electrophotographic photosensitive member evaluation apparatus (manufactured by Yamanashi Electronics Co., Ltd.), the electrostatic potential such as the initial surface potential, sensitivity, residual potential, dark decay rate, etc. of the electrophotographic photosensitive member produced by Examples and Comparative Examples The characteristics were measured, and all were good characteristics.

[0113] [Image Evaluation]

 The following printing tests were carried out on the electrophotographic photoreceptors produced in the examples and comparative examples: o

 The electrophotographic photosensitive member is negatively charged by the roller charging method (contact charging method), and mounted on an electrophotographic device that forms images by LED exposure, non-magnetic one-component development method, and blade cleaning method. , 000 sheets were intermittently printed, and the image after printing was evaluated. The results are shown in Table 1.

 [0114] The presence or absence of occurrence of positive memory was visually evaluated for the first printed image in the image evaluation and the printed image after printing a predetermined number of sheets. Further, after printing a predetermined number of sheets, it was visually checked whether toner filming occurred on the surface of the electrophotographic photosensitive member. The results are shown in Table 1.

 [0115] [Measurement of surface roughness]

 Ten-point average roughness Rz of the surface of the electrophotographic photosensitive member produced in Examples and Comparative Examples was measured using a contact type surface roughness meter. The measurement was performed before and after printing the image evaluation. The results are shown in Table 1. The 10-point average roughness Rz before printing is about the same in both the examples and comparative examples. . Met.

[0116] [Measurement of film loss]

For the photosensitive layer of the electrophotographic photosensitive member prepared in the examples and comparative examples, contact The film thickness was measured using a tactile film thickness meter. The measurement was performed before and after printing the image evaluation. Film reduction after printing Ad is the value obtained by subtracting the film thickness d after printing from the film thickness d before printing.

 0 1

The The results are shown in Table 1.

[Table 1] Image test results

表 1から明らかなように、画像評価における実施例 1〜12は所定枚数印字後の膜 厚減少が少なく、電気特性に悪影響を与えない。また、ポジメモリー及びトナーフィル ミング、黒スジが発生せず、良好な印字画像であった。

As is apparent from Table 1, Examples 1 to 12 in image evaluation have little decrease in film thickness after printing a predetermined number of sheets and do not adversely affect electrical characteristics. Also, no positive memory, toner filming or black streaks occurred, and the printed image was good.

Claims

An electrophotographic photosensitive member in which a photosensitive layer having at least a charge generating agent, a charge transfer agent, and a binder resin is formed on a conductive support, and a general formula ( 1. An electrophotographic photoreceptor comprising a polycarbonate copolymer containing the repeating unit represented by 1) and a compound represented by the general formula (2) as a charge transfer agent. General formula (1) [Chemical 1]

 [Wherein R and R are each independently a hydrogen atom, halogen atom, trifluoromethyl group, carbon  1 2 Either an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms A is an integer of 1 to 200, X is O—, or the following general formula (3) or (3 ′) (wherein R is a hydrogen atom, a halogen atom, a trifluoromethyl group,  Three Either an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms And b and b ′ are each independently an integer of 0 to 6, and c is an integer of 0 to 4. X represents 0-, or the following general formula (4) or (4 ') (wherein  2  R is a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, Four Or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms. ), And f and f are each independently an integer of 0 to 6, and 1 is an integer of 0 to 4. General formula (3) [Chemical 2]

General formula (3 ')  [Chemical R R 3] (CH ₂ ) _b , general formula (4)  [Chemical 4] (C

General formula (4 ')  [Chemical 5] (CH ₂ ) _f NH General formula (2)  [Chemical 6]

[Wherein R to R each independently represent hydrogen, a halogen atom, or a carbon atom which may have a substituent 1  5 9  Represents an alkyl group of ˜6, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and d represents an integer of 0 or 1. ]  [2] The electrophotographic photosensitive member according to [1], comprising a polycarbonate copolymer having a structure represented by the general formula (5).  General formula (5) [Chemical 7] — 0 ~ R31― (CF ^ _e ― R ₃₂ [In the formula, R is an alkylene group, an arylene group having 6 to 12 carbon atoms, or a substituted arylene group.  31 Any one of them, R represents a hydrogen atom or a fluorinated alkyl group, e is an integer of 1 to 20  32 Represents. ]  2. The electrophotographic photosensitive member according to claim 1, comprising a polycarbonate copolymer containing a repeating unit represented by the general formula (6).  General formula (6) [Chemical 8]

[In the formula, R to R each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number.  33 36  It represents any of 6 to 12 aryl groups or substituted aryl groups, and g, h and i each independently represent an integer of 0 to 4. ]  2. The electrophotographic photosensitive member according to claim 1, comprising a polycarbonate copolymer containing a repeating unit represented by the general formula (7). General formula (7) [Chemical 9]

(Wherein R and R are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, carbon  37 38 Represents any of the aryl groups or substituted aryl groups of formulas 6 to 12, and each m is independently 0 to Represents an integer of 4. j and k are the straight chain numbers of saturated hydrocarbons and are integers of 1-20. 2. The electrophotographic photosensitive member according to claim 1, comprising a polycarbonate copolymer containing a repeating unit represented by the general formula (8). General formula (8) [Chemical 10]

[Wherein R 1 to R 4 are each independently a halogen atom, an alkyl group having 1 to 12 carbon atoms,  39 42 Represents a hexyl group, an aryl group having 6 to 12 carbon atoms, or a substituted aryl group, and B represents a single bond, —O—, —CO—, —S—, —SO—, or —SO—. P, q, r  2 And s is an integer from 0 to 4. ]  2. The electrophotographic photosensitive member according to claim 1, comprising a charge transfer agent having a structure represented by the general formula (9). General formula (9) [Chemical 11]

[Wherein R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms which may have a substituent.  10 11 R 1 represents either a hydrogen atom or a dialkylamino group. ] 2. The electrophotographic photosensitive member according to claim 1, comprising a charge transfer agent having a structure represented by the general formula (10).  General formula (10)  [Chemical 12]

[Wherein R to R each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.  13 16  And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ]  2. The electrophotographic photosensitive member according to claim 1, comprising a charge transfer agent having a structure represented by the general formula (11).  General formula (11)  [Chemical 13]

[Wherein R to R each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.  17 20  And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ] [9] The electrophotographic photosensitive member according to [1], comprising a charge transfer agent having a structure represented by the general formula (12).  General formula (12) [Chemical 14]

[Wherein R 1 to R 4 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.  21 24 Represents a group, an alkoxy group, or an aryl group that may have a substituent, and R represents a hydrogen atom, a halogen atom, an alkyl group or alkoxy group having 1 to 6 carbon atoms, twenty five It represents either a aryl group having a substituent, a alkenyl group or a alkadienyl group having a substituent, or general formula (12 ′), and t is 0 or 1. Represents an integer. ] General formula (12 ')  [Chemical 15]

(In the formula, R and R are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.  26 27 Or an aryl group, or an aryl group, and w represents an integer of 0 or 1. )  2. The electrophotographic photoreceptor according to claim 1, comprising a charge transfer agent having a structure represented by the general formula (13). General formula (13) [Chemical 16]

[Wherein R 1 to R 4 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.  21 24 Represents a group, an alkoxy group, or an aryl group that may have a substituent, and R represents a hydrogen atom, a halogen atom, an alkyl group or alkoxy group having 1 to 6 carbon atoms, twenty five It represents a cycloalkyl group or a alkaryl group or a alkadenyl group having a substituent. ]