JP2005215025A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high sensitivity and high durability, without cleaning faults, even if it is used repeatedly by maintaining high image quality due to improvement in the resistance to abrasion. <P>SOLUTION: The photoreceptor includes on at least a surface a layer hardening a copolymer with polymerization compound, having (meta)acryloiloxy which has a specific substitution silyl group and specific triarylamine structure. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an electrophotographic photosensitive member containing an alkoxylane and copolymerized with a triarylamine copolymer in a photosensitive layer and cured, and an image forming apparatus and a process cartridge using the same. The present invention relates to a long-life electrophotographic photosensitive member.
The electrophotographic photosensitive member of the present invention and the electrophotographic process using the same are applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine, and the like.

  In recent years, there has been a demand for higher durability of photoconductors as electrophotographic copying machines and electrophotographic printers become faster, smaller, and have higher image quality. In the electrophotographic process, the durability of the photoconductor deteriorates due to mechanical and chemical effects in the repeated processes of charging, exposure, development, transfer, and cleaning. Mechanical degradation causes wear and scratches on the photoreceptor, and chemical degradation causes oxidation degradation of the binder resin and charge transfer agent due to the generated ozone, and image quality degradation due to deposits and the like. In addition, as described above, the diameter of the photoconductor is reduced with the increase in speed and size, and the use conditions in the electrophotographic process become severe. The contact pressure is inevitably increased, which causes wear of the photoconductor, turning of the rubber blade, and blade noise (abnormal noise). Furthermore, cleaning failure has occurred with finer toner particles due to the demand for higher image quality, and improvement in toner releasability from the photoreceptor has been demanded. The wear of the photoconductor causes problems such as potential color fluctuations in color images due to potential fluctuations and sensitivity fluctuations, and problems in color reproducibility.

Many cured films using a silane coupling agent have been proposed to improve the durability of these photoreceptors. For example, although a charge transport material having an alkoxysilane group has been proposed in Patent Document 1 (Japanese Patent Laid-Open No. 10-095787), there is concern about the occurrence of cracks due to volume shrinkage, and the charge transport material volume is large and rigid. There is a hindrance to molecular motion during curing, a large amount of unreacted silanol remains, the resistance decreases with humidity, and image blurring is expected under high humidity. Further, a polymer compound having an alkoxysilane group, a silane coupling agent, and a charge transport material having a methylol group or a trimethoxysilyl group have been proposed in Patent Document 2 (Japanese Patent Laid-Open No. 2003-241409). Charge transport materials with little increase in potential and bright part potential have many aromatic rings substituted, and when added alone, they crystallize during film formation, and phase separation results in formation of an opaque or uneven film. Sensitivity and cleaning Insufficient blades are generated.
JP-A-10-095787 JP2003-241409A

  An object of the present invention is to provide a high-sensitivity, high-durability electrophotographic photosensitive member that maintains high image quality by improving wear resistance and that does not have poor cleaning even when used repeatedly.

（式中、Ｒ^１、Ｒ^５は水素、あるいはメチル基を表し、Ｒ^２、Ｒ^３、Ｒ^４はメチル基、メトキシ基を表し、但しＲ^２、Ｒ^３、Ｒ^４のうち少なくとも２個はメトキシ基であり、Ｘは単結合、−ＣＯＯ−を表し、Ａｒ^１は置換、未置換アリレン基を表し、Ａｒ^２、Ａｒ^３は同一又は異なる置換、未置換アリール基を表し、ａ、ｂは共重合重量比を表し、０．１≦ａ≦０．９、０．１≦ｂ≦０．９、であり、ｎは１０から１０００の整数を表す。）
（２）下記一般式（２）で表される高分子化合物を硬化させてなる層を少なくとも表面に有することを特徴とした電子写真感光体、

（式中、Ｒ^６、Ｒ^１０は水素、あるいはメチル基を表し、Ｒ^７、Ｒ^８、Ｒ^９はメチル基、メトキシ基を表し、但しＲ^７、Ｒ^８、Ｒ^９のうち少なくとも２個はメトキシ基であり、Ｚは単結合、−ＣＯＯ−を表し、Ａｒ^４、Ａｒ^５は置換、未置換アリレン基を表し、Ａｒ^６、Ａｒ^７は同一又は異なる置換、未置換アリール基を表し、Ｙは単結合、酸素原子、

で表され、Ｒ^２０は水素、炭素数１から４のアルキル基、置換、未置換のアリール基を表し、ｅは１から４の整数、ｆは１または２の整数を表し、ｃ、ｄは共重合重量比を表し、０．１≦ｃ≦０．９、０．１≦ｄ≦０．９、であり、ｍは１０から１０００の整数を表す。）
（３）前記硬化層がさらに下記一般式（３）で示されるシランカップリング剤を含有し硬化されている前記（１）、または前記（２）記載の電子写真感光体、

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４は炭素数１から１２の直鎖状、あるいは分岐状のアルキル基またはフェニル基、アミノ基置換アルキル基、炭素数１から４の直鎖状、あるいは分岐状のアルコキシ基、アセトキシ基を表す。但しＲ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４のうちの少なくとも１つは前記アルコキシ基を表す。） As a result of intensive studies, the present inventors have found that it is effective to contain a surface layer composed of a cured product of a specific polymer compound having a triarylamine structure and an alkoxyl group in the photosensitive layer. Invented.
That is, the present invention
(1) An electrophotographic photoreceptor having at least a layer formed by curing a polymer compound represented by the following general formula (1),

(Wherein R ¹ and R ⁵ represent hydrogen or a methyl group, R ² , R ³ and R ⁴ represent a methyl group and a methoxy group, provided that at least two of R ² , R ³ and R ⁴ are A methoxy group, X represents a single bond, —COO—, Ar ¹ represents a substituted or unsubstituted arylene group, Ar ² and Ar ³ represent the same or different substituted or unsubstituted aryl groups, and a and b are (Represents copolymerization weight ratio, 0.1 ≦ a ≦ 0.9, 0.1 ≦ b ≦ 0.9, and n represents an integer of 10 to 1000)
(2) An electrophotographic photoreceptor having at least a layer formed by curing a polymer compound represented by the following general formula (2),

(In the formula, R ⁶ and R ¹⁰ represent hydrogen or a methyl group, R ⁷ , R ⁸ and R ⁹ represent a methyl group and a methoxy group, provided that at least two of R ⁷ , R ⁸ and R ⁹ are A methoxy group, Z represents a single bond, —COO—, Ar ⁴ and Ar ⁵ represent a substituted and unsubstituted arylene group, Ar ⁶ and Ar ⁷ represent the same or different substituted and unsubstituted aryl groups, Y Is a single bond, oxygen atom,

R ²⁰ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group, e represents an integer of 1 to 4, f represents an integer of 1 or 2, and c and d are It represents a copolymerization weight ratio, 0.1 ≦ c ≦ 0.9, 0.1 ≦ d ≦ 0.9, and m represents an integer of 10 to 1000. )
(3) The electrophotographic photosensitive member according to (1) or (2), wherein the cured layer further contains a silane coupling agent represented by the following general formula (3) and is cured.

(In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a straight chain having 1 to 12 carbon atoms, or a branched alkyl group or phenyl group, an amino group-substituted alkyl group, and a straight chain having 1 to 4 carbon atoms. Or a branched alkoxy group or acetoxy group, provided that at least one of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represents the alkoxy group.)

(4) In an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, the silicone represented by the general formula (1) or the general formula (2) is formed in at least one layer from the surface side most distant from the conductive substrate. An electrophotographic photoreceptor containing the compound,
(5) Said (1), (2), or (3) which hydrolyzed the silicone copolymer which consists of the said General formula (1) or General formula (2) with an acidic catalyst, and was hardened | cured under heating after coating. ) Electrophotographic photosensitive member as described above,
(6) The electrophotographic photosensitive member according to any one of (1) to (5), wherein the photosensitive member has a belt shape, a sheet shape, or a drum shape.
(7) An image forming apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is any one of (1) to (5). An image forming apparatus,
(8) An image forming apparatus main body integrally supporting the electrophotographic photosensitive member according to any one of (1) to (5) and at least one unit selected from a charging unit, a developing unit, and a cleaning unit. The present invention relates to a process cartridge for an image forming apparatus, which is detachable from the image forming apparatus.

The photoreceptor having a silicone cured surface layer obtained by curing the specific copolymer of the present invention is a highly durable photoreceptor excellent in mechanical properties, and generation of cracks is not confirmed even after repeated use.
Further, there is no generation of image flow under the high humidity characteristic of the cured silicone film, and a high quality image can be formed.

The polymer compound represented by the general formulas (1) and (2) of the present invention has a molecular weight of 1,000 to 200,000, preferably 5,000 to 100,000, by GPC. Specific examples of the polymer compound will be described below based on the general formula (1).
In the general formulas (2) and (3), a) an alkyl group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ²⁰ is a straight chain such as a methyl group, an ethyl group, a propyl group, or an i-propyl group. Or a branched alkyl group, and a methyl group is preferred from the viewpoint of ease of synthesis.

In the general formulas (1) and (2), Ar ² , Ar ³ , Ar ⁶ and Ar ⁷ are aryl groups. Specific examples thereof include a non-condensed carbocyclic group, a condensed polycyclic hydrocarbon group, and a hetero group. A cyclic group is mentioned.
The condensed polycyclic hydrocarbon group preferably has 18 or less carbon atoms forming a ring, for example, a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, s-indacenyl group, fluorenyl group, acenaphthylenyl group, pleyadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylyl group, pyrenyl group, Examples include a chrycenyl group and a naphthacenyl group.

  In addition, as the non-condensed carbocyclic group, a monovalent group of a monocyclic hydrocarbon compound such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether and diphenyl sulfone, or biphenyl, polyphenyl, diphenylalkane, diphenylalkene, diphenylalkyne, Monovalent groups of non-condensed polycyclic hydrocarbon compounds such as triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane, and polyphenylalkene, or ring assemblies such as 9,9-diphenylfluorene And monovalent groups of hydrocarbon compounds.

Furthermore, when it is a heterocyclic group, specific examples include monovalent groups such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.
The aryl group represented by Ar ² or Ar ³ may have a substituent shown below.
A halogen atom, a cyano group, a nitro group, an alkyl group, preferably a C1 to C12, especially a C1 to C8, more preferably a C1 to C4 linear or branched alkyl group, and these alkyl groups further include a fluorine atom , A hydroxyl group, a cyano group, a C1-C4 alkoxy group, a phenyl group or a halogen atom, a C1-C4 alkyl group or a C1-C4 alkoxy group may be substituted. Specifically, methyl group, ethyl group, n-butyl group, i-propyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl Group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like.

Furthermore, the aryl groups represented by Ar ² and Ar ³ may have the following substituents.
Alkoxy group (—OR ¹⁵ ): R ¹⁵ represents an alkyl group as defined in a). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, benzyloxy group And a trifluoromethoxy group.
Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. This may contain a C1-C4 alkoxy group, a C1-C4 alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.

：（式中、Ｒ^１６及びＲ^１７は各々独立に水素原子、前記一般式（２）で定義したアルキル基、またはアリール基を表し、アリール基としては、例えばフェニル基、ビフェニル基又はナフチル基が挙げられ、これらはＣ１〜Ｃ４のアルコキシ基、Ｃ１〜Ｃ４のアルキル基またはハロゲン原子を置換基として含有してもよい。Ｒ^１６及びＲ^１７は共同で環を形成してもよい）
具体的には、アミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（トリール）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ピロリジノ基等が挙げられる。
メチレンジオキシ基、又はメチレンジチオ基等のアルキレンジオキシ基又はアルキレンジチオ基、等が挙げられる。
以上の置換基の他、置換又は無置換のスチリル基、置換無置換のβ−フェニルスチリル基ジフェニルアミノフェニル基、ジトリルアミノフェニル基等も挙げることができる。 Alkyl mercapto group or aryl mercapto group: Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(In the formula, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group defined in the general formula (2), or an aryl group, and examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. These may contain a C1-C4 alkoxy group, a C1-C4 alkyl group or a halogen atom as a substituent. R ¹⁶ and R ¹⁷ may form a ring together)
Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And pyrrolidino group.
Examples thereof include an alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.
In addition to the above substituents, a substituted or unsubstituted styryl group, a substituted and unsubstituted β-phenylstyryl group diphenylaminophenyl group, a ditolylaminophenyl group, and the like can also be mentioned.

で表され、Ｒ^２０は水素、炭素数１から４のアルキル基、置換、未置換のアリール基〔前記Ａｒ²、Ａｒ³、Ａｒ^６、Ａｒ^７で表されるアリール基〕を表し、ｅは２から４の整数、ｆは１または２の整数を表す。 The arylene group represented by Ar ¹ , Ar ⁴ , and Ar ⁵ is a divalent group derived from the aryl group represented by Ar ² , Ar ³ , Ar ⁶ , Ar ⁷ .
Y is a single bond, an oxygen atom,

R ²⁰ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group [the aryl group represented by Ar ² , Ar ³ , Ar ⁶ , Ar ⁷ ], and e is An integer of 2 to 4, f represents an integer of 1 or 2.

The production methods of the general formulas (1) and (2) are, for example, the following triarylamine-containing vinyl monomer or acrylic monomer and 3-methacryloyloxypropyltrimethoxysilane (LS-3380) commercially available from Shin-Etsu Chemical Co., Ltd. ), 3-methacryloyloxypropyldimethoxymethylsilane (LS-3375) and the like. Copolymerization is carried out by a known method such as solution polymerization in the presence of a radical polymerization initiator to obtain a copolymer.
The copolymerization ratio was such that (meth) acryloyloxymethoxysilane: triarylamine-containing compound was copolymerized at a weight ratio of 0.1 to 0.9: 0.1 to 0.9, and (meth) acryloyloxymethoxysilane was copolymerized. When the polymerization ratio is high, a film having a high hardness can be obtained. However, the decrease in triarylamine sites tends to reduce the charge transport ability and increase the bright part potential and the residual potential. The copolymerization ratio is determined in consideration of the balance.

  Polymerization solvents are aromatic systems such as toluene, ketone systems such as methyl isobutyl ketone, and ester systems such as butyl acetate, especially because triarylamine monomers dissolve in these solvents, but acrylic oil methoxysilane monomers Is soluble in alcohol solvents, and becomes soluble in alcohol when methoxy groups are hydrolyzed and silanol is formed. Therefore, in aromatic solvents, ketone solvents, mixed solvents of ester solvents and isopropyl alcohol. Polymerization is desirable.

As the polymerization initiator, azo initiators such as azobisisobutyronitrile and azobisisovaleronitrile, and peroxides such as benzoyl peroxide are used.
Copolymers may be copolymerized with acrylic acid as an intramolecular hydrolysis catalyst for methoxysilane, glycidyl methacrylate for improved adhesion, and butyl methacrylate for imparting flexibility to prevent cracks in the cured film. .

Specific examples of the copolymerizable triarylamine-containing compound are shown below, but are not limited thereto.

  These copolymers are hydrolyzed and thermally cured by using an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid alone or a metal catalyst such as dibutyltin acetic acid.

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４は炭素数１から１２の直鎖状、あるいは分岐状のアルキル基またはフェニル基、アミノ基置換アルキル基、炭素数１から４の直鎖状、あるいは分岐状のアルコキシ基、アセトキシ基を表す。但しＲ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４のうちの少なくとも１つは前記アルコキシ基を表す。） A silane coupling agent represented by the following general formula (3) may be added to the copolymer.

(In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a straight chain having 1 to 12 carbon atoms, or a branched alkyl group or phenyl group, an amino group-substituted alkyl group, and a straight chain having 1 to 4 carbon atoms. Or a branched alkoxy group or acetoxy group, provided that at least one of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represents the alkoxy group.)

In general, trialkoxy compounds can provide high hardness, but unreacted silanol remains and the surface resistance tends to decrease due to moisture adhesion at high humidity. Tends to decrease and the strength decreases. In consideration of this, that is, these coupling agents are preferably selected in consideration of film hardness and humidity dependency.
Examples of the silane coupling agent represented by the general formula (3) include tetramethoxysilane, tetraacetoxysilane, tetraethoxysilane, tetraallyloxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrakis (2-methoxy). Ethoxy) silane, tetrabutoxysilane, tetraphenoxysilane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, trimethoxysilane, methyltrimethoxysilane, trimethoxyvinylsilane, ethyltrimethoxysilane, tri Ethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, methyltriacetoxysilane, butyltrimethoxysilane, methyltriethoxysilane, Lutris (2-aminoethoxy) silane, triacetoxyvinylsilane, ethyltriacetoxysilane, triethoxyvinylsilane, ethyltriethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, allyltriethoxysilane 3-allylthiopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-allylaminopropyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, 3-aminopropyltriethoxysilane, methyltriisopropyl Penoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperazinopropyltrimethoxysilane, methyltripropo Sisilane, methyltris (2-methoxyethoxysilane), 3- [2- (2-aminoethylaminoethylamino) propyl] triethoxysilane, tris (1-methylvinyloxy) vinylsilane, 2- (3,4-epoxycyclohexyl) Ethyl) trimethoxysilane, triisopropoxyvinylsilane, tris (2-methoxyethoxy) vinylsilane, 3-piperidinopropyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, 3- (2-methylpiperidinopropyl) ) Trimethoxysilane, 3-cyclohexylaminopropyltrimethoxysilane, benzyltriethoxysilane, 3-benzylaminopropyltrimethoxysilane, tetradecyltrichlorosilane, octyltriethoxysilane, phenyltri (2-methoxyethoxy) silane, 3- (vinylbenzylaminopropyl) trimethoxysilane, 3- (vinylbenzylaminopropyl) triethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane, dimethoxymethylsilane, dimethoxydimethylsilane , Diethoxysilane, diethoxymethylsilane, diethoxydimethylsilane, dimethoxy-3-mercaptopropylmethylsilane, diacetoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydivinylsilane, diethoxydiethylsilane, dimethyl Dipropoxysilane, 3-aminopropyldiethoxymethylsilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, dimethoxymethylsilane Nylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, dimethoxymethyl-2-piperidinoethylsilane, dimethoxymethyl-3-piperazinopropylsilane, dibutoxydimethyl Silane, 3-dimethylaminopropyldiethoxymethylsilane, diethoxymethylphenylsilane, dimethoxymethyl-3-piperidinopropylsilane, dimethoxymethyl-3- (4-methylpiperidinopropyl) silane, dimethoxydiphenylsilane, dimethoxy Phenyl-2-piperidinoethoxysilane, diacetoxydiphenylsilane, diethoxydiphenylsilane, diethoxydodecylmethylsilane, diphenylmethoxy-2-piperidinoethoxysilane, docosyl Chill dichlorosilane, diethoxy methyl octadecyl silane and the like.
These coupling agents are added in an amount of 0.2 to 0.7 parts, preferably 0.3 to 0.5 parts, based on 1 part of the solid content of the copolymer.

The photoreceptor will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view showing an electrophotographic photosensitive member of the present invention. A photosensitive layer 103 containing at least a charge generating substance and a charge transporting substance is provided on a conductive support 101. Further, the general formula (1 ) Or a photosensitive layer 401 containing a cured product of the polymer compound (2) and a charge generation material, that is, the photosensitive layer 102 is composed of 103 and 401.

  FIG. 2 shows a charge generation layer 201 mainly composed of a charge generation material, a charge transport layer 203 mainly composed of a low molecular charge transport material and a binder resin, and a general formula (1). This is a case where the polymer compound is cured or the polymer compound cured charge transport layer 301 represented by the general formula (2) is used, and the cured layer may contain an organic or inorganic filler.

  In FIG. 3, an intermediate layer 302 is provided on a conductive support 101, on which a charge generation layer 201 mainly composed of a charge generation material, and a charge transport layer 203 mainly composed of a low molecular charge transport material and a binder resin. And a polymer compound cured by the general formula (1) or a polymer compound cured charge transport layer 301 represented by the general formula (2), wherein the cured layer is made of an organic or inorganic filler. You may contain.

Examples of the conductive support 101 include those having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, indium oxide, etc. The metal oxide of the above is coated with film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel or the like and extruded by drawing or drawing. After pipe formation, surface treatment pipes such as cutting, superfinishing, and polishing can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Laid-Open No. 52-36016 can be used as the conductive support 101.

  In addition, a material obtained by dispersing conductive powder in an appropriate binder resin and coating it on the support can also be used as the conductive support 101 of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done.

  The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin.

Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support 101 of the present invention.

Next, the photosensitive layer will be described. The photosensitive layer may be a single layer or a laminated layer, but for convenience of explanation, the case where it is composed of the charge generation layer 201 and the charge transport layer 203 will be described first.
First, the charge generation layer 201 will be described.
The charge generation layer 201 is a layer mainly composed of a charge generation material, and a binder resin may be used as necessary. As the charge generation material, inorganic materials and organic materials can be used.

  Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.

  On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having fluorenone skeleton, azo pigments having oxadiazole skeleton, azo pigments having bis-stilbene skeleton, azo pigments having distyryl oxadiazole skeleton, azo pigments having distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Jigoido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  The binder resin used as necessary for the charge generation layer 201 includes polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, and poly-N-vinylcarbazole. Polyacrylamide is used. These binder resins can be used alone or as a mixture of two or more. Furthermore, you may add a charge transport material as needed.

Charge transport materials include hole transport materials and electron transport materials.
Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophene-4-one, 1,3,7-trinitro Examples thereof include electron accepting substances such as dibenzothiophene-5,5-dioxide. These electron transport materials can be used alone or as a mixture of two or more.

  Examples of the hole transporting material include the electron donating materials shown below and are used favorably. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline , Phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, and the like. These hole transport materials can be used alone or as a mixture of two or more.

As a method for forming the charge generation layer 201, a vacuum thin film manufacturing method and a casting method from a solution dispersion system can be largely mentioned. As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed. In addition, in order to provide the charge generation layer by the casting method described later, the inorganic or organic charge generation material described above is used together with a binder resin, if necessary, with a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone, ball mill, atom It can be formed by dispersing with a lighter, sand mill or the like and applying the solution after diluting the dispersion appropriately. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like.
The film thickness of the charge generation layer 201 provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

The charge transport layer will be described.
In the layer structure shown in FIG. 2, the charge transport layer 203 is mainly composed of a low molecular charge transport material and a binder resin. Examples of the low molecular charge transport material include oxazole derivatives and oxadiazole derivatives (Japanese Patent Laid-Open No. 52-139065). 52-139066) imidazole derivatives, triphenylamine derivatives (described in Japanese Patent Application No. 1-77839), benzidine derivatives (described in Japanese Patent Publication No. 58-32372), α-phenylstilbene derivatives (Japanese Patent 57-73075), hydrazone derivatives (described in JP-A Nos. 55-154955, 55-156955, 55-52063, 56- and the like), triphenylmethane derivatives (described in JP-B No. 51-10983), Anthracene derivatives (described in JP-A-51-94829), styryl derivatives (JP-A-56-56) It described 29245,58-198043), according to the carbazole derivative (JP 58-), or the like can be used pyrene derivatives (described in Japanese Patent Application No. 2).

  Binder resin has good film properties (bisphenol A type, bisphenol Z type, bisphenol C type), or their copolymers, polyarylate, polysulfone, polyester, methacrylic resin, polystyrene, vinyl acetate, epoxy resin, phenoxy resin. Etc. are used. It is formed by dissolving, coating, and drying together with a charge transport material and a binder resin.

  The amount of these low-molecular charge transport materials is 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge transport layer 203 is preferably 30 μm or less from the viewpoint of resolution and responsiveness. Regarding the lower limit, although it differs depending on the system to be used (particularly the charging potential), it is preferably 5 μm or more.

  As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. These may be used alone or in combination of two or more.

  A coating containing a polymer compound represented by the general formula (1) or (2) is applied on the charge transport layer 203 to provide the cured polymer compound film. In this case, the paint can also contain a filler. Examples of the organic filler material include fluorine resin powder such as polytetrafluoroethylene, silicone resin powder, a-carbon powder, and the like. Metal oxides such as silica, tin oxide, zinc oxide, titanium oxide, alumina, zirconium oxide, indium oxide, antimony oxide, bismuth oxide, calcium oxide, antimony-doped tin oxide, tin-doped indium oxide, fluorine Examples thereof include metal fluorides such as tin fluoride, calcium fluoride, and aluminum fluoride, and inorganic materials such as potassium titanate and boron nitride. Among these fillers, the use of inorganic fillers is advantageous for improving the wear resistance from the viewpoint of the hardness of the fillers.

Furthermore, as the filler effective for improving the image quality, a filler having high electrical insulation is preferable, and silica, titanium oxide, alumina, zinc oxide, zirconium oxide and the like can be used particularly effectively. Two or more kinds of these fillers or other fillers can be mixed. It is also possible to use a mixture of two or more fillers having a dielectric constant of 5 or less and fillers having a dielectric constant of 5 or more.
Further, these fillers can be surface-treated with at least one kind of surface treatment agent, and it is preferable from the viewpoint of dispersibility of the fillers. Decreasing the dispersibility of the filler not only increases the residual potential, but also decreases the transparency of the coating, causes defects in the coating, and decreases the wear resistance. It can develop into a big problem.

As the surface treatment agent, all conventionally used surface treatment agents can be used, but a surface treatment agent capable of maintaining the insulating properties of the filler is preferable. For example, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, a higher fatty acid, etc., or a mixing treatment of these with a silane coupling agent, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Silicone, aluminum stearate, or the like, or a mixed treatment thereof is preferable in terms of filler dispersibility. Although the treatment with the silane coupling agent is somewhat reduced in resistance, the influence may be suppressed by applying a mixing treatment of the surface treatment agent and the silane coupling agent. The surface treatment amount varies depending on the average primary particle size of the filler used, but is preferably 3 to 30 wt%, more preferably 5 to 20 wt%. This paint is applied by a dipping method, a spray method, or a ring method, and then cured by light or heat energy to produce a cured layer 301 having a thickness of 1 to 10 μm.

  FIG. 3 shows a configuration in which an intermediate layer 302 is provided on a conductive support 101. The intermediate layer is provided to prevent charge injection, coating defects, and moire, and is a resin layer, a pigment dispersion layer, or an aluminum support. As an alumite layer, such resins include water-soluble resins such as polyvinyl alcohol, casein, and polyacrylic acid, alcohol-soluble resins such as copolymerizable nylon and methoxymethylated nylon, polyurethane, and melamine resins. Curable resins that form a three-dimensional network structure, such as alkyd-melamine resins and epoxy resins. The pigment dispersion is obtained by dispersing fine powders of metal oxides, metal sulfides, metal nitrides, and the like, which can be exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like.

Furthermore, as the intermediate layer 302 of the present invention, a metal oxide layer formed by using, for example, a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like is also useful. In addition to this, the undercoat layer of the present invention is formed by anodizing aluminum oxide, organic matter such as polyparaxylylene (parylene), SiO, SnO ₂ , TiO ₂ , ITO, CeO _2, etc. What provided the inorganic substance with the vacuum thin film preparation method can also be used favorably.
On the intermediate layer 302, the charge generation layer 201, the charge transport layer 203, and the cured layers 301 of the general formulas 1 and 2 described in FIG.

  In the present invention, a plasticizer and a leveling agent may be added to the photosensitive layer and the charge transport layer. As the plasticizer, those used as a plasticizer in general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin. is there.

  The photosensitive layer 102 is composed of a charge generation material, a low molecular charge transport material, and a binder resin. As the binder resin, in addition to the binder resin previously described for the charge transport layer 203, the binder resin described for the charge generation layer 201 is used. And a hardened layer 401 of the polymer compound and the charge generation material represented by the general formula (1) or (2) is formed on the layer 103. Moreover, you may add a cyclic ether compound, a polyether compound, a diphenoquinone derivative etc. as an antistatic agent, and 0.5-10 weight part is preferable with respect to 100 weight part of binder resin.

  The photosensitive layer 102 is formed by applying a coating solution obtained by dispersing the above materials with a disperser using a solvent such as tetrahydrofuran, dioxane, dichloroethane, or cyclohexane by a dip coating method, spray coating, bead coating, ring coating, or the like. Can be formed. The film thickness of the photosensitive layer is suitably about 5 to 25 μm.

  In the present invention, an antioxidant may be added for the purpose of preventing the decrease in sensitivity and the increase in residual potential, in order to improve environmental resistance. The antioxidant may be added to any layer containing an organic substance, but good results are obtained when it is added to a layer containing a charge transport material. Preferred examples of such antioxidants are listed below.

Monophenol compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate and the like.
Bisphenol compounds 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4′- Thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol) and the like.

High molecular phenol compound 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' -Bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] cricol ester, tocopherols and the like.

Paraphenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N , N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine, and the like.

Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2 -Octadecenyl) -5-methylhydroquinone and the like.

Organic sulfur compounds dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.
Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant in the present invention is 0.1 to 100 parts by weight, preferably 2 to 30 parts by weight with respect to 100 parts by weight of the charge transport material.

FIG. 4 is a schematic diagram for explaining the electrophotographic process and the electrophotographic apparatus of the present invention, and the following examples also belong to the category of the present invention.
In FIG. 4, the photoreceptor 1 has at least a photosensitive layer provided on a conductive support, and has at least a triarylamine cured layer as an outermost surface layer. The photosensitive member 1 has a drum shape, but may be a sheet shape or an endless belt shape. As the charging charger 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13, a corotron, a scorotron, a solid charger (solid state charger), a charging roller, or the like is used, and known means are used. All are usable.

As the transfer means, the above charger can be generally used. However, as shown in the figure, a combination of a transfer charger and a separation charger is effective.
The light source such as the image exposure unit 5 and the charge removal lamp 2 emits light such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL). All things can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

In addition to the steps shown in FIG. 4, the light source and the like are provided with a transfer step, a static elimination step, a cleaning step, a pre-exposure step and the like using light irradiation, so that the photosensitive member is irradiated with light.
The toner developed on the photosensitive member 1 by the developing unit 6 is transferred to the transfer paper 9, but not all is transferred, and some toner remains on the photosensitive member 1. Such toner is removed from the photoreceptor by the fur brush 14 and the blade 15. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

When a positive (negative) charge is applied to the electrophotographic photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. When this is developed with negative (positive) polarity toner (electrodetection fine particles), a positive image can be obtained, and when developed with positive (negative) polarity toner, a negative image can be obtained.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.
The toner is colorized and is composed of cyan, magenta, and yellow. Since these toners generally require fluidity when replenishing the toner, a fluidizing agent such as silica or titanium oxide is added.

FIG. 5 shows another example of an electrophotographic process and apparatus according to the present invention. The photoreceptor 21 is a belt-like member in which a photosensitive layer having at least a triarylamine cured layer at least on the outermost surface layer is provided on a conductive support. This belt-like photosensitive member is driven and supported by driving rollers 22a and 22b, and is charged by a charger 23, image exposure by a light source 24, development (not shown), transfer using a charger 25, pre-cleaning exposure by a light source 26, Cleaning with the brush 27 and static elimination with the light source 28 are repeated. In FIG. 5, the photoconductor 21 (of course, the support is translucent in this case) is irradiated with pre-cleaning exposure light from the support side.
The belt photoconductor and the driving / supporting roller can be integrated into a unit so that it can be freely attached to and detached from the apparatus.

FIG. 6 shows an example of a process cartridge used in the present invention.
A charging roller 3 as a charging unit, a developing unit 6 for supplying an appropriate amount of developer to the surface of the photoconductor, and a cleaning unit 16 having a blade as a unit for cleaning the surface of the photoconductor after image transfer are integrally formed around the photoconductor 1. It has been incorporated.
This cartridge is formed so that it can be detachably handled by an image forming apparatus equipped with means necessary for image formation such as optical writing means, transfer means, static elimination means, fixing means, and recording paper transport means. .
The photoreceptor 1 mounted on the cartridge has at least a photosensitive layer on a conductive support, and has at least a triarylamine cured layer on the outermost surface layer.

Hereinafter, the present invention will be described by way of examples.
Polymerization example 1
3-methacryloyloxypropyltrimethoxysilane (LS-3380 manufactured by Shin-Etsu Chemical Co., Ltd.) 30 g, V-17 30 g, toluene 40 g, isopropyl alcohol (IPA) 20 g, azobisisobutyronitrile (AIBN) 0.4 g The flask was removed and stirred for 30 minutes in a nitrogen stream, heated to 70 ° C., reacted for 5 hours, then heated to 80 ° C. and reacted for 3 hours. A light yellow copolymer having a viscosity of 580 cp was obtained.
Similarly, copolymerization was carried out according to the formulation shown in Table 1 below.

１０部
塩化メチレン １００部
〔硬化層用塗工液〕
重合例１の共重合体 ２０部
テトラエトキシシラン ２部
トリメトキメチルシシラン ４部
５％硫酸水溶液 １部
メタノール ５部
この処方液を密栓下一晩放置した後リング塗工で塗工し、１３０℃で１時間硬化させた。 Example 1
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, a charge transport layer coating solution, and a cured layer sequentially on a φ30 mm aluminum cylinder, an undercoat of 3.5 μm is applied. An electrophotographic photosensitive member of the present invention was obtained by forming a layer, a 0.2 μm charge generation layer, a 22 μm charge transport layer, and a 5 μm cured layer.
[Coating liquid for undercoat layer]
Alkyd resin (Beccosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals)
6 parts Melamine resin (Super Becamine G-821-60, manufactured by Dainippon Ink and Chemicals)
4 parts Titanium oxide 40 parts Methyl ethyl ketone 200 parts [Coating liquid for charge generation layer]
Oxotitanium phthalocyanine pigment 2 parts Polyvinyl butyral (UCC: XYHL) 0.2 part Tetrahydrofuran 50 parts [Coating liquid for charge transport layer]
Polycarbonate resin (Z Polyca, Tv Kasei Mv50,000) 10 parts

10 parts Methylene chloride 100 parts [Coating liquid for hardened layer]
Copolymer of Polymerization Example 1 20 parts Tetraethoxysilane 2 parts Trimethoxymethyl silane 4 parts 5% sulfuric acid aqueous solution 1 part Methanol 5 parts This formulation solution was allowed to stand overnight under a tight stopper and then coated by ring coating. Cured for 1 hour at ° C.

Examples 2-7
In the same manner as in Example 1, an undercoat layer, a charge generation layer, and a charge transport layer were provided on a φ30 mm aluminum cylinder, and a cured layer of 5 μm as shown in Table 2 below was provided.

８部
ポリカーボネート樹脂（Ｚポリカ、帝人化成社製 Ｍｖ５万） １０部
ジクロルメタン ９０部 Comparative Example 1
In the same manner as in Example 1, an intermediate layer and a charge generation layer were provided, and then the following charge transport layer solution was ring-coated to provide a 25 μm charge transport layer.

8 parts Polycarbonate resin (Z Polyca, Tv Kasei Mv50,000) 10 parts Dichloromethane 90 parts

Next, the photoconductors of Examples 1 to 7 and the photoconductor of Comparative Example 1 were loaded into the process cartridge shown in FIG. 6 and a durability test for 10,000 sheets was performed with an Ricoh Imagio MF200 copier. As the exposure light source, 650 nm laser light was used. The results are shown in Table 2.
The initial dark part potential (VD) was -600V, and the initial bright part potential (VL) was -150V. ΔVD and ΔVL in the table are the amounts of change from the initial potential, and were obtained as follows.
ΔVD = | VD (10,000 sheets) |-| VD (initial) |
ΔVL = | VL (at 10,000 sheets) |-| VL (initial) |
After the endurance test for 10,000 sheets, copying was performed in a high-temperature and high-humidity environment at 30 ° C. and 90%, and an image quality test was performed.
The amount of wear was measured with a Fischer eddy current film thickness meter before and after the run.

２２部
シクロヘキサノン ４００部
次いで、上記ミルベースをメチルエチルケトン９００部で希釈して電荷発生層塗工液とした。
〔電荷輸送層用塗工液〕
下記組成を溶解し調整した。
ポリスチレン（ＭＷ１Ｃ 東洋スチレン社製） １２部

１２部
ジクロルメタン ９０部
１％シリコーンオイル（ＫＦ５０信越シリコーン社製）ジクロルメタン溶液
１部
中間層、電荷発生層、電荷輸送層を設けた上に下記処方の塗料をリング法で塗工し、１３０℃で４０分間硬化させ硬化電荷輸送層３μｍを設けた。
重合例１の共重合体 ２０部
アルミナ（スミコランダムＡＡ０３ 住友化学社） ２部
セロソルブアセテート ５部
の処方液はジルコニアメディアを用いて３時間振動ミルを行い分散した、この液１２部にテトラエトキシシラン２部、トリメトキシメチルシラン３部、２％硫酸水溶液０．５部を添加、混合して塗料とした Example 8
A solution consisting of 10 parts of polyamide resin (CM8000 manufactured by Toray Industries, Inc.), 220 parts of methanol, and 100 parts of n-butanol was dip coated at 5 mm / sec on a 30 mm aluminum cylinder, dried at 100 ° C. for 10 minutes, and 0.3 μm. An intermediate layer was provided.
Next, the following dispersion was applied by dip coating and dried at 120 ° C. for 10 minutes to provide a 0.2 μm charge generation layer. The following charge transport layer coating solution was dip coated and dried at 120 ° C. for 20 minutes to provide a 20 μm charge transport layer.
A 15 cm ball mill pot was charged with the following charge generating material and solvent, and ball milled for 48 hours using zirconia media having a diameter of 10 mm, and then 500 parts of cyclohexanone was added to adjust the mill base.

22 parts Cyclohexanone 400 parts Next, the mill base was diluted with 900 parts of methyl ethyl ketone to obtain a charge generation layer coating solution.
[Coating liquid for charge transport layer]
The following composition was dissolved and adjusted.
Polystyrene (MW1C, manufactured by Toyo Styrene Co., Ltd.) 12 parts

12 parts Dichloromethane 90 parts 1% Silicone Oil (KF50 Shin-Etsu Silicone) Dichloromethane solution
1 part An intermediate layer, a charge generation layer, and a charge transport layer were provided, and a paint having the following formulation was applied by a ring method and cured at 130 ° C. for 40 minutes to provide a cured charge transport layer of 3 μm.
Copolymer of Polymerization Example 1 20 parts Alumina (Sumicorundum AA03 Sumitomo Chemical Co., Ltd.) 2 parts Cellosolve acetate 5 parts of the prescription liquid was dispersed by performing a vibration mill for 3 hours using zirconia media. Tetraethoxysilane was dispersed in 12 parts of this liquid. 2 parts, 3 parts of trimethoxymethylsilane, 0.5 part of 2% aqueous sulfuric acid solution were added and mixed to form a paint.

Example 9
In the same manner as in Example 8, an intermediate layer, a charge generation layer, and a charge transport layer were provided, and a paint having the following formulation was applied by the ring method and cured at 130 ° C. for 40 minutes to provide a cured charge transport layer of 3 μm.
Copolymer of Polymerization Example 2 20 parts Silica (manufactured by KMPX Shin-Etsu Chemical Co., Ltd.) 2 parts Cellosolve acetate 5 parts of the prescription liquid was dispersed by performing a vibration mill for 3 hours using zirconia media. Tetraethoxysilane 2 was dispersed in 12 parts of this liquid. Part, 3 parts of trimethoxymethylsilane, 0.5 part of 2% sulfuric acid aqueous solution were added and mixed to obtain a paint.
As a result of conducting a durability test of 10,000 sheets of the photoconductors of Examples 8 and 9 as in Example 1, no flaws were observed on the surface of the photoconductor, and the wear amount was 0. No flow was observed.

８部
ポリカーボネート樹脂（ＴＳ２０５０ 帝人化成社） １０部
ジクロルメタン ９０部
下記硬化電荷輸送層液をスプレー法で塗工し、１３０℃で３０分間硬化し、３μｍの硬化層を設けた。
重合例３の共重合体 ２０部
トリメトキシメチルシラン ４部
ジメトキシジメチルシラン ２部
２％硫酸水溶液 ０．５部
メタノール １５部 Example 10
The support was replaced with a cylindrical nickel belt having a thickness of 30 μm, a circumference of 180 mm, and a belt width of 340 mm prepared from an aluminum cylinder by electroforming, and the following charge was provided on the same intermediate layer and charge generation layer as in Example 1. An endless belt-shaped photoconductor was prepared by providing a transport layer and a cured layer.
The following charge transport layer coating solution was applied by a dipping method and dried at 130 ° C. for 30 minutes to provide a 20 μm charge transport layer.

8 parts Polycarbonate resin (TS2050 Teijin Chemicals Co., Ltd.) 10 parts Dichloromethane 90 parts The following cured charge transport layer solution was applied by a spray method and cured at 130 ° C. for 30 minutes to provide a 3 μm cured layer.
Copolymer of polymerization example 3 20 parts Trimethoxymethylsilane 4 parts Dimethoxydimethylsilane 2 parts 2% sulfuric acid aqueous solution 0.5 parts Methanol 15 parts

Example 11
In the same manner as in Example 10, an intermediate layer, a charge generation layer, and a charge transport layer were provided on a nickel belt, and the following cured layer coating solution was applied by a spray method, cured at 130 ° C. for 30 minutes, and 3 μm A cured charge transport layer was provided.
Copolymer of Polymerization Example 4 20 parts Trimethoxymethylsilane 4 parts Dimethoxydimethylsilane 2 parts 2% aqueous sulfuric acid solution 0.5 parts Methanol 15 parts

Comparative Example 2
A comparative photoreceptor of 25 μm was prepared by providing an undercoat layer, a charge generation layer, and a charge transport layer in the same manner as in Example 10 except that the cured charge transport layer was not provided.

The belt photoreceptors of Examples 10 and 11 and Comparative Example 2 were subjected to image evaluation using the image forming apparatus shown in FIG. At that time, the endless belt photoconductor is supported and driven by two drive rollers having a diameter of 20 mm, and the two rollers and the photoconductor are unitized so as to be detachable from the electrophotographic apparatus (hereinafter referred to as a photoconductor magazine). Write down). As a writing light source, a laser having a 650 nm oscillation was used, and the photoreceptor surface potential was initially set to -800V, and the exposure portion potential during the entire surface exposure was set to -100V.
For development, reversal development was performed using a two-component developer composed of a negatively charged toner and a carrier.
The evaluation items are as follows.
a) Evaluation of 10,000 images under normal temperature and normal humidity (22-25 ° C., 40-60% RH) environment,
b) After leaving the photoconductor magazine in a room temperature and humidity environment for 1 month, evaluation of crack resistance and image of the photoconductor c) After leaving the photoconductor magazine in an environment of 30 ° C. and 85% for 2 weeks, Crack resistance evaluation and image evaluation,

Explanatory drawing of the layer structure in the Example of this invention photoreceptor. Explanatory drawing of the layer structure in another Example same as the above. Explanatory drawing of the layer structure in another Example same as the above. 1 is a schematic diagram illustrating an electrophotographic process and an electrophotographic apparatus of the present invention. Schematic which shows another example same as the above. FIG. 2 is a schematic view showing an example of a process cartridge of the present invention.

Claims (8)

An electrophotographic photosensitive member having at least a layer formed by curing a polymer compound represented by the following general formula (1).

(Wherein R ¹ and R ⁵ represent hydrogen or a methyl group, R ² , R ³ and R ⁴ represent a methyl group and a methoxy group, provided that at least two of R ² , R ³ and R ⁴ are A methoxy group, X represents a single bond, —COO—, Ar ¹ represents a substituted or unsubstituted arylene group, Ar ² and Ar ³ represent the same or different substituted or unsubstituted aryl groups, and a and b are Represents a copolymerization weight ratio, 0.1 ≦ a ≦ 0.9, 0.1 ≦ b ≦ 0.9, and n represents an integer of 10 to 1000.) An electrophotographic photosensitive member having a layer formed by curing a polymer compound represented by the following general formula (2) on at least a surface.

(In the formula, R ⁶ and R ¹⁰ represent hydrogen or a methyl group, R ⁷ , R ⁸ and R ⁹ represent a methyl group and a methoxy group, provided that at least two of R ⁷ , R ⁸ and R ⁹ are A methoxy group, Z represents a single bond, —COO—, Ar ⁴ and Ar ⁵ represent a substituted and unsubstituted arylene group, Ar ⁶ and Ar ⁷ represent the same or different substituted and unsubstituted aryl groups, Y Is a single bond, oxygen atom,

R ²⁰ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group, e represents an integer of 1 to 4, f represents an integer of 1 or 2, and c and d are It represents a copolymerization weight ratio, 0.1 ≦ c ≦ 0.9, 0.1 ≦ d ≦ 0.9, and m represents an integer of 10 to 1000. ) The electrophotographic photosensitive member according to claim 1, wherein the cured layer further contains a silane coupling agent represented by the following general formula (3) and is cured.

(In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a straight chain having 1 to 12 carbon atoms, or a branched alkyl group or phenyl group, an amino group-substituted alkyl group, and a straight chain having 1 to 4 carbon atoms. Or a branched alkoxy group or acetoxy group, provided that at least one of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represents the alkoxy group.)   In the electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, the silicone compound represented by the general formula (1) or the general formula (2) is contained in at least one layer from the surface side farthest from the conductive substrate. Electrophotographic photoreceptor.   The electrophotographic photosensitive member according to claim 1, 2, or 3, wherein the silicone copolymer comprising the general formula (1) or the general formula (2) is hydrolyzed with an acidic catalyst and cured under heating after coating.   6. The electrophotographic photosensitive member according to claim 1, wherein the shape of the photosensitive member is a belt shape, a sheet shape, or a drum shape.   6. An image forming apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is one according to any one of claims 1 to 5. An image forming apparatus.   6. The electrophotographic photosensitive member according to claim 1 and at least one unit selected from a charging unit, a developing unit, and a cleaning unit are integrally supported and detachable from the main body of the image forming apparatus. A process cartridge for an image forming apparatus.

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