JP2006321752A - New silyl compound, electrophotographic photoreceptor given by using the same, image forming device, and process cartridge for image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound from which a layer having abrasion resistance and not causing release is obtainable, and to provide a highly durable photoreceptor given by using the same. <P>SOLUTION: This compound is expressed by general formula 1 (R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each a 1-3C alkoxy or the like; Ar<SP>1</SP>and Ar<SP>2</SP>are each an aryl or the like; X is a single bond or the like; and m and n are each an integer of 1 to 5). The electrophotographic photoreceptor contains the compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel photofunctional organic silyl compound useful for an organic electronic device, particularly an electrophotographic photosensitive member, and an electrophotographic photosensitive member, an image forming apparatus, and a process cartridge for the image forming apparatus using the same.

  In recent years, electrophotographic photoreceptors using organic photoconductive materials and organic electronic devices such as organic electroluminescence elements (organic EL elements) have attracted attention in terms of productivity, ease of material design, safety, Various improvements have been put into practical use. From the viewpoint of stabilizing and extending the life of these organic electronic devices, for example, in organic electroluminescence elements, materials that do not cause a change in film morphology due to the generated Joule heat, and in electrophotographic photoreceptors, ozone, NOx, etc. There is a need for materials that are stable against physical stresses such as heat and mechanical force, as well as chemical stability.

In particular, electrophotographic photoreceptors are highly demanded for stabilization of charging characteristics and longer life.
In recent years, an electrophotographic photosensitive member has been mainly separated from the charge generation layer and the charge transport layer from the viewpoint of sensitivity and stability. It consists of two layers: a layer formed by binding a resin as a binder, and a layer obtained by dispersing or dissolving the charge transport material in the binder resin. As the binder for the charge transport layer, mainly hole transport materials have been studied, and as the binder, thermoplastic resins such as polycarbonate resin, polyester resin, acrylic resin and polystyrene resin, and thermosetting resins such as urethane resin and epoxy resin. Is being considered.

  In this case, it is necessary to charge the surface of the charge transport layer negatively by corona charging or roller charging. Deterioration of the resin due to ozone generated at that time, wear due to electric shock due to discharge on the surface of the photoreceptor, sensitivity reduction, charging There is a problem that the characteristics of the photosensitive member are deteriorated due to various causes such as deterioration in performance, subsequent toner development, transfer to paper, mechanical destruction due to friction during cleaning, and the like.

  Therefore, in order to increase the strength of the charge transport layer, or to prevent surface adhesion and improve the cleaning property, it has been attempted to blend a polysiloxane resin with a copolymer component or another resin. Using a thermosetting resin containing a charge transport layer (see Patent Document 1), having a protective layer containing a polysiloxane resin (see Patent Document 2), silica gel, urethane resin, fluorine in a thermosetting polysiloxane resin A resin is dispersed as a protective layer (see Patent Document 3), a resin in which a thermosetting polysiloxane resin is dispersed in a thermoplastic resin is used as a protective layer or a charge transport material binder resin (see Patent Document 4), etc. Has been proposed. These are properties that are not found in other resins, such as transparency, dielectric breakdown resistance, light stability, and low surface tension of polysiloxane resins. It is intended to improve.

However, since the polysiloxane resin has extremely poor compatibility with organic compounds, it is not used alone as a charge transport material constituent resin, and for modification of the charge transport material constituent resin by copolymerization or blending. Even when used in the above, there is a problem that phase separation occurs when the amount of the polysiloxane resin is increased.
Therefore, in order to use the polysiloxane resin alone as a binder constituting the charge transport layer, it is necessary to find a charge transport material soluble in the polysiloxane resin.

Patent Document 5 adopts a method in which not a polysiloxane resin but a monomer is applied and dried to form a resin after heating. However, this has a problem of electrical characteristics, and Patent Documents 6 and 7 propose a cured film of a photofunctional organosilicon compound containing a hydroxyl group and a silane coupling agent. Patent Document 8, Patent Document 9, Patent Document 10, and Patent Document 11 disclose photofunctional organosilicon compounds in which these photofunctional organosilicon compounds are derived from a charge transport material having a vinyl group and alkoxysilane. Yes. Patent Document 12 discloses a cured film of a triarylamine photofunctional organosilicon compound obtained by a reaction between a triarylaminephenol compound and an alkoxysilane isocyanate compound. Patent Document 13 discloses a photofunctional organosilicon compound derived using a Grignard reaction, Patent Document 14, Patent Document 15, and Patent Document 16 describe a photofunctional organosilicon compound derived using a Wittig reaction, Patent Document No. 17 shows photofunctional organosilicon compounds derived by carboxylic esterification, and these photofunctional organosilicon compounds can obtain a high-hardness surface layer by a curing reaction. However, internal stress is stored in the film due to volume shrinkage during film formation, and when stress is applied from the outside, it becomes brittle and brittle fractures, resulting in a peeling phenomenon.
Japanese Patent Laid-Open No. 61-238062 JP-A-62-108260 JP-A-4-346356 JP-A-4-273252 JP 2000-221723 A JP 2000-310870 A JP 2003-241409 A Japanese Patent Application Laid-Open No. 9-124942 Japanese Patent Laid-Open No. 9-124943 JP-A-9-127710 JP-A-9-190004 Japanese Patent Laid-Open No. 3-191358 JP 11-124387 A JP-A-10-251277 JP-A-11-171890 JP-A-11-180987 Japanese Patent Laid-Open No. 11-236391

  The present invention relates to a compound that provides a wear-resistant and non-peeling layer that relaxes internal stress due to volume shrinkage during curing and also reduces external stress, and a highly durable photoconductor using the compound that maintains high image quality. The purpose is to provide.

｛式中、Ｒ^１、Ｒ^２、Ｒ^３は炭素数１〜３のアルコキシ基、炭素数１〜５のアルキル基、又はフェニル基を表し、アルコキシ基は２個以上である。Ａｒ^１、Ａｒ^２は同一又は異なる置換もしくは無置換のアリール基を表し、Ｘは単結合、酸素原子、−ＣＯＯ−、

（Ｒ^４は水素、アルキル基、又はアリール基を、ａは２〜４の整数を、ｂは１または２を表す）を表し、ｍ、ｎは１〜５の整数を表す。） As a result of intensive studies to solve the above problems, it has been found that the above problems can be solved by finding a novel silyl compound and using it in the photosensitive layer. That is, the present invention has the following configuration.
(1) A silyl compound represented by the following general formula 1.

{Wherein R ¹ , R ² and R ³ represent an alkoxy group having 1 to ³ carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and the number of alkoxy groups is two or more. Ar ¹ and Ar ² represent the same or different substituted or unsubstituted aryl group, X is a single bond, an oxygen atom, —COO—,

(R ⁴ represents hydrogen, an alkyl group, or an aryl group, a represents an integer of 2 to 4, and b represents 1 or 2), and m and n represent an integer of 1 to 5. )

｛Ａｒ^１、Ａｒ^２は同一又は異なる置換もしくは無置換のアリール基を表し、Ｘは単結合、酸素原子、−ＣＯＯ−、

（Ｒ^４は水素、アルキル基、又はアリール基を、ａは２〜４の整数を、ｂは１または２を表す）を表し、ｍは１〜５の整数を表す。｝

（Ｒ^１、Ｒ^２、Ｒ^３は炭素数１〜３のアルコキシ基、炭素数１〜５のアルキル基、又はフェニル基を表し、アルコキシ基は２個以上であり、ｎは１〜５の整数を表す。） (2) The silyl compound according to (1), which is synthesized from an alcohol compound represented by the following general formula 2 and an isocyanate compound represented by the following general formula 3.

{Ar ¹ and Ar ² represent the same or different substituted or unsubstituted aryl groups, and X represents a single bond, an oxygen atom, —COO—,

(R ⁴ represents hydrogen, an alkyl group, or an aryl group, a represents an integer of 2 to 4, and b represents 1 or 2), and m represents an integer of 1 to 5. }

(R ¹ , R ² , R ³ represent an alkoxy group having 1 to ³ carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, the alkoxy group is 2 or more, and n is an integer of 1 to 5 Represents.)

（Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はアリール基を表し、少なくとも１個はアルコキシ基である。） (3) An electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, comprising the silyl compound according to (1) or (2) and / or a cured product thereof.
(4) The electrophotographic photosensitive member according to (3), wherein the cured product is obtained by curing the silyl compound and a compound represented by the following general formula 4.

(R ⁵ , R ⁶ , R ⁷ and R ^{8 each} represent a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group, and at least one is an alkoxy group.)

(5) The photosensitive layer is a laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated, and the charge transport layer contains the silyl compound and / or a cured product thereof (3) Or an electrophotographic photoreceptor according to (4).
(6) The above (3) or (4), wherein the electrophotographic photoreceptor has a protective layer on a photosensitive layer, and the protective layer contains the silyl compound and / or a cured product thereof. The electrophotographic photosensitive member described.
(7) The electrophotographic photosensitive member according to any one of (3) to (6), wherein the shape of the photosensitive member is a belt shape, a sheet shape, or a drum shape.

(8) In the image forming apparatus including at least a charging unit, an image exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member, the electrophotographic photosensitive member according to any one of (3) to (6). An image forming apparatus which is an electrophotographic photosensitive member.
(9) The image forming apparatus main body integrally supports the electrophotographic photosensitive member according to any one of (3) to (6) and at least one unit selected from a charging unit, a developing unit, and a cleaning unit. A process cartridge for an image forming apparatus, wherein the process cartridge is removable.

  The silyl compound represented by the general formula 1 of the present invention is a photofunctional silyl compound having a charge transport property, a curing reaction, a high hardness, and having a urethane bond and a methylene chain, and having a urethane bond between the urethane bond sites. It is possible to relieve internal stress due to volume shrinkage at the time of curing by secondary structure and methylene chain, and to form a layer having no wear resistance and exfoliation in which external stress is relieved. Accordingly, the electrophotographic photoreceptor using the novel silyl compound of the present invention is a highly durable photoreceptor excellent in mechanical durability and maintaining high image quality.

The present invention is a photofunctional silyl compound represented by the following general formula 1.

（Ｒ^４は水素、アルキル基、又はアリール基を、ａは２〜４の整数を、ｂは１または２を表す）を表し、ｍ、ｎは１〜５の整数を表す。 ^Wherein, R ^1, R 2, ^{R 3} is an alkoxy group having 1 to 3 carbon atoms, an alkyl group, or a phenyl group having 1 to 5 carbon atoms, an alkoxy group is 2 or more. Ar ¹ and Ar ² represent the same or different substituted or unsubstituted aryl group, X is a single bond, an oxygen atom, —COO—,

(R ⁴ represents hydrogen, an alkyl group, or an aryl group, a represents an integer of 2 to 4, and b represents 1 or 2), and m and n represent an integer of 1 to 5.

The alkyl group is a linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom. , A phenyl group substituted with a C1-C4 alkyl group or a C1-C4 alkoxy group may be contained. 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.
The alkoxy group represents a linear or branched alkoxy group having 1 to 3 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and the like.

In the general formula 1, Ar ¹ and Ar ² are aryl groups, and specific examples thereof include a non-condensed carbocyclic group, a condensed polycyclic hydrocarbon group, and a heterocyclic group.
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 ¹ and Ar ² may have a substituent shown below.
(1) halogen atom, cyano group, nitro group (2) alkyl group, preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and these alkyl groups Is further substituted with a fluorine atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. It may contain. 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.

(3) Alkoxy group (—OR ¹⁰ ): R ¹⁰ represents an alkyl group defined in (2). 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.
(4) 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.
(5) Alkyl mercapto group or aryl mercapto group: Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

（式中、Ｒ^１１及びＲ^１２は各々独立に水素原子、（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、これらは炭素数１〜４のアルコキシ基、炭素数１〜４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^１１及びＲ^１２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。 (6)

(Wherein R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group defined in (2), or an aryl group, and examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. May contain, as a substituent, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ¹¹ and R ¹² may jointly form a ring.
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.

(7) An alkylenedioxy group such as a methylenedioxy group or a methylenedithio group, or an alkylenedithio group.
(8) Substituted or unsubstituted styryl group, substituted and unsubstituted β-phenylstyryl group diphenylaminophenyl group, ditolylaminophenyl group, and the like.

Examples of the compound represented by the general formula 1 include the following.

Ａｒ^１、Ａｒ^２は同一又は異なる置換もしくは無置換のアリール基を表し、Ｘは単結合、酸素原子、−ＣＯＯ−、

（Ｒ^４は水素、アルキル基、又はアリール基を、ａは２〜４の整数を、ｂは１または２を表す）を表し、ｍは１〜５の整数を表す。 The compound represented by the general formula 1 is obtained by reacting an alcoholic compound represented by the following general formula 2 with an isocyanate compound represented by the following general formula 3 using an ether, aromatic, ester or ketone solvent. be able to. Preferably, it can be obtained by reacting at 25 to 50 ° C. for 5 to 40 hours in a ketone-based dehydrated solvent. The end point of the reaction proceeds while confirming disappearance with -NCO and -OH from the infrared absorption spectrum.

Ar ¹ and Ar ² represent the same or different substituted or unsubstituted aryl group, X is a single bond, an oxygen atom, —COO—,

(R ⁴ represents hydrogen, an alkyl group, or an aryl group, a represents an integer of 2 to 4, and b represents 1 or 2), and m represents an integer of 1 to 5.

Ｒ^１、Ｒ^２、Ｒ^３は炭素数１〜３のアルコキシ基、炭素数１〜５のアルキル基、又はフェニル基を表し、アルコキシ基は２個以上であり、ｎは１〜５の整数を表す。

R ¹ , R ² , and R ³ represent an alkoxy group having 1 to ³ carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, the alkoxy group is 2 or more, and n is an integer of 1 to 5 To express.

The silyl compound represented by the general formula 1 of the present invention itself has a charge transporting ability and can also be used as a charge transporting substance.
The silyl compound represented by the general formula 1 of the present invention is a photofunctional silyl compound that undergoes a curing reaction, has high hardness, and has a urethane bond and a methylene chain, and has a secondary structure and a methylene chain between urethane bond sites. It is possible to relieve internal stress due to volume shrinkage at the time of curing due to, and to form a layer having no wear resistance and peeling, in which external stress is relieved.
When curing, the alkoxysilane is hydrolyzed with an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, an organic acid such as oxalic acid, acetic acid or trifluoroacetic acid, or a catalyst such as dibutyltin diacetate or aluminum III2,4-pentanedionate. The cured film is obtained by dehydrating and condensing as silanol by heating at 50 to 200 ° C. for 10 to 60 minutes.

一般式４でのＲ^５、Ｒ^６、Ｒ^７、Ｒ^８は水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はアリール基を表し、少なくとも１個はアルコキシ基である。 The compound represented by the general formula 1 may be used alone, or may be used in combination with a silane coupling agent represented by the following general formula 4.

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula 4 represent a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group, at least one of which is an alkoxy group is there.

  Specifically, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, diphenylsilanediol , Phenyltriethoxysilane, tetraethoxysilane, ethyltrimethoxysilane, diethoxydimethylsilane, triethoxysilane, diethyldiethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, triethoxyvinylsilane, allyltriethoxysilane, tetrapropoxy Silane, propyltriethoxysilane, methyltripropoxysilane, dibutoxydimethylsilane, tetrabutoxysilane, Tiltlyisopropoxysilane, methyltris (2-methoxyethoxy) silane, 3-mercaptopropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethoxy-3,3,3-trifluoropropylsilane And benzyltriethoxysilane.

  The silyl compounds represented by the general formulas 1 and 4 have 1 to 4 alkoxy groups and are highly reactive, and hydrolyze with water, an acid catalyst, a base catalyst, and an organometallic catalyst to form silanols. It cures by condensation reaction. When there are many preparations of one alkoxy group, the degree of cross-linking decreases and the hardness decreases, and when there are many preparations of four alkoxy groups, the degree of cross-linking increases and the hardness increases, but due to the life of the coating solution and the solid polymer reaction Since unreacted silanol remains, it causes humidity dependency and causes blurring of the image. Therefore, the preparation amount and addition amount of 1 to 4 alkoxy groups are appropriately determined. Although depending on the number of alkoxy groups, for example, 0.2 to 1.2 parts by weight of the compound represented by the general formula 4 can be used with respect to 1 part by weight of the silyl compound represented by the general formula 1. Moreover, the silyl compound of General formula 1 and General formula 4 may form a film property with polycarbonate, polystyrene, methacrylic resin, polyester, alkyd resin, melamine resin, epoxy resin, polyvinyl butyral, phenoxy resin, acrylic polyol, and the like. it can.

The photoconductor will be described.
Examples of the conductive substrate include those having a volume resistance of 10 ¹⁰ Ω or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, and iron, and oxides such as tin oxide and indium oxide. Coated with a film or cylindrical plastic, paper or the like by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc. I. , I. I. It is possible to use pipes that have been surface treated by cutting, superfinishing, polishing, etc., after forming into a bare pipe by a method such as extrusion or drawing.

The photosensitive layer in the present invention may be either a single layer type or a laminated type. For convenience of explanation, a laminated type having a charge generation layer and a charge transport layer will be described first.
First, the charge generation layer will be described. The charge generation layer 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 carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having 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.

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

  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.

Methods for forming the charge generation layer include a vacuum thin film preparation method and a casting method from a solution dispersion system.
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 latter casting method, the above-described inorganic or organic charge generation material is used together with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone, ball mill, atom or the like. It can be formed by dispersing with a lighter, sand mill or the like and applying the solution after diluting the dispersion appropriately. The coating can be performed using a dip coating method, a spray coating method, a bead coating method, or the like.
The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

Next, the charge transport layer will be described.
The silyl compound represented by the general formula 1 of the present invention has a charge transport function and may be cured by itself to form a charge transport layer, or may be cured together with the compound represented by the general formula 4 to form a charge transport layer. It may be formed. Further, it can be dissolved and coated together with a binder resin to form a charge transport layer. In particular, when the charge transport layer is a surface layer of an electrophotographic photoreceptor, it is preferable to cure because the wear resistance is improved by curing.
Binder resins include polycarbonate (bisphenol A type, bisphenol Z type, bisphenol C type, or copolymers thereof), polyarylate, polysulfone, polyester, methacrylic resin, polystyrene, vinyl acetate, epoxy resin, phenoxy resin, alkyd resin, Melamine resin, epoxy resin, polyvinyl butyral, acrylic polyol, and the like are used. These binders can be used alone or as a mixture of two or more.

  The silyl compound represented by the general formula 1 can also be added to a conventional molecular dispersion charge transport layer. Examples of low molecular charge transport materials used in the charge transport layer include oxazole derivatives, oxadiazole derivatives (described in JP-A Nos. 52-139065 and 52-139066), imidazole derivatives, and triphenylamine derivatives. (Described in Japanese Patent Application No. 1-77839), benzidine derivatives (described in Japanese Patent Publication No. Sho 58-), α-phenylstilbene derivatives (described in Japanese Patent Application Laid-Open No. 57-73075), hydrazone derivatives (Japanese Patent Application Laid-Open No. Sho 55). -154955, JP-A-55-15694, JP-A-55-52063, JP-A-56-81850, etc.), triphenylmethane derivatives (described in JP-B-51-10983) , Anthracene derivatives (described in JP-A-51-94829), styryl derivatives (JP-A-56-2924). 58-198043), carbazole derivatives (described in JP-A-58-58552), pyrene derivatives (described in Japanese Patent Application No. 2-94812), and the like, and the above binder resins can be used. .

Examples of the polymer charge transport material used in the charge transport layer include a carboat resin having a triarylamine skeleton in the main chain or side chain described in JP-A-9-319120, and JP-A-5-202135. Examples thereof include acrylic resins having a triarylamine skeleton, polyvinyl carbazole and the like, and the silyl compound of the present invention can also be added to these polymer charge transport layers.
The thickness of the charge transport layer is suitably about 5 to 100 μm, and preferably about 10 to 40 μm.

  In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer. As the plasticizer, those used as plasticizers for 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. It is.

  Moreover, the silyl compound of this invention can be used also as a protective layer of a cured film with the compound shown by General formula 1 and General formula 4 on the conventional molecular dispersion charge transport layer. In this case, it behaves as a conventional charge transport and there is no inconvenience, and the charge transport layer has nothing.

Next, the case where the photosensitive layer has a single layer structure will be described.
When a single-layer photosensitive layer is provided by the casting method, in many cases, a silyl compound represented by the general formula 1 of the present invention or a silyl compound represented by the general formula 1 and a compound represented by the general formula 4 is used as a charge transport material. It is formed from a cured layer composed of a charge generating material and a binder resin. The charge generating material is added in 2 to 10% by weight in the layer, the silyl compound of general formula 1 is added in 30 to 70% by weight, the silyl compound of general formula 4 is added in 0 to 50% by weight, and the binder resin is added in 20 to 50% by weight. In this case, a mineral acid, an organic acid, an organometallic compound, or the like is used as a catalyst.
As the charge generation material, the charge generation materials listed above for the charge generation layer can be used.
As the binder resin, the binder resin previously mentioned in the charge transport layer may be used as it is, or the binder resin mentioned in the charge generation layer may be mixed and used.
Moreover, a plasticizer and a leveling agent can also be added as needed.
The film thickness of the single-layer photoconductor is suitably about 5 to 100 μm, and preferably about 10 to 40 μm.

  In the electrophotographic photoreceptor used in the present invention, an undercoat layer can be provided between a conductive substrate and a photosensitive layer (a charge generation layer in the case of a laminated type). The undercoat layer is provided for the purpose of improving adhesiveness, preventing moire and the like, improving the coatability of the upper layer, and reducing the residual potential. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is applied with a solvent on these resins, the resin may be a resin having a high resistance to a general organic solvent. desirable.

  Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and polyacrylic acid, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, and epoxy resin. Examples thereof include curable resins that form a three-dimensional network structure. Further, fine powders such as metal oxides exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like, or metal sulfides and metal nitrides may be added. These undercoat layers can be formed using an appropriate solvent and coating method as in the photosensitive layer described above.

Furthermore, a metal oxide layer formed by, 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 as the undercoat layer of the present invention.
In addition, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodic oxidation, organic substances such as polyparaxylylene (parylene), SiO, SnO ₂ , TiO ₂ , ITO, CeO _2. A material provided with an inorganic material such as a vacuum thin film can also be used favorably. The thickness of the undercoat layer is suitably from 0 to 5 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.

The following are mentioned as antioxidant which can be used for this invention.
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.

Hereinafter, an image forming apparatus and a process cartridge for an image forming apparatus according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view for explaining an electrophotographic process and an image forming apparatus according to the present invention. The following examples also belong to the category of the present invention.
In FIG. 1, a photoreceptor 1 is provided with at least a photosensitive layer on a conductive substrate and contains the compound represented by the general formula 1 and / or a cured product thereof. 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 state charger (solid state charger), a charging roller, or the like is used. All are usable.

As the transfer means, the above charger can be generally used. However, as shown in the figure, a combination of the transfer charger 10 and the separation charger 11 is effective.
In addition, light sources such as the image exposure unit 5 and the charge removal lamp 2 emit 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. 1, 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 at the time of toner replenishment, fluidizing agents such as silica and titanium oxide are added.

FIG. 2 shows another example of an electrophotographic process and apparatus according to the present invention. The photosensitive member 21 is a belt-shaped member in which at least a photosensitive layer is provided on a conductive substrate and contains the compound represented by the general formula 1 and / or a cured product thereof. This belt-like photoconductor 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. 2, the photosensitive member 21 (of course, the substrate is translucent in this case) is irradiated with pre-cleaning exposure light from the substrate 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. 3 shows an example of a process cartridge used in the present invention.
A charging roller 33 as a charging unit, a developing unit 34 for supplying an appropriate amount of developer to the surface of the photoconductor, and a cleaning unit 35 having a blade as a unit for cleaning the surface of the photoconductor after image transfer are integrally formed around the photoconductor 31. 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 31 mounted on the cartridge includes at least a photosensitive layer on a conductive substrate and contains the compound represented by the general formula 1 and / or a cured product thereof.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all. In addition, a part shows a weight part.

上記ヒドロキシエチルオキシ体８．１９ｇ（０．０２ｍｏｌ）、テトラヒドロフラン２０ｍｌ、３−（トリエトキシシリル）プロピルイソシアネート４．９４ｇ（０．０２ｍｏｌ）を三角フラスコに取り、密封し室温で４０時間攪拌した、未反応のイソシアネートに基づく赤外吸収スペクトル２２７０ｃｍ^−１が確認されるものの反応を終了させた。析出物をろ別し、ろ液は減圧下テトラヒドロフランを除き、シリカゲル／トルエン：酢酸エチル＝２：１ｖｏｌでカラムクロマトで目的のシリル化合物６ｇ（４５．６％）、ｍ．ｐ．：７１〜７３℃を得た。（Ｎｏ．２のシリル化合物） Example 1

8.19 g (0.02 mol) of the hydroxyethyloxy compound, 20 ml of tetrahydrofuran, and 4.94 g (0.02 mol) of 3- (triethoxysilyl) propyl isocyanate were placed in an Erlenmeyer flask, sealed and stirred at room temperature for 40 hours. Although the infrared absorption spectrum 2270 cm ⁻¹ based on the isocyanate of the reaction was confirmed, the reaction was terminated. The precipitate was filtered off, the filtrate was freed from tetrahydrofuran under reduced pressure, and 6 g (45.6%) of the desired silyl compound was obtained by column chromatography with silica gel / toluene: ethyl acetate = 2: 1 vol. p. : 71-73 degreeC was obtained. (No. 2 silyl compound)

ａ：７．４９−７．３７ｐｐｍ（４Ｈ）、
ｂ：７．０７−６．９４ｐｐｍ（ｍ １２Ｈ）、
ｃ：５．０３ｐｐｍ（１Ｈ）、
ｄ：４．４１ｐｐｍ（２Ｈ）、
ｅ：４．１８ｐｐｍ（２Ｈ）、
ｆ：３．８４−３．７９ｐｐｍ（６Ｈ）、
ｇ：３．２−３．１７（２Ｈ）
ｈ：２．３１（６Ｈ）、
ｉ：１．６１ｐｐｍ（２Ｈ）、
ｊ：１．２４ｐｐｍ（９Ｈ）、
ｋ：０．６５−０．６１ｐｐｍ（２Ｈ） The ¹ H-NMR spectrum of the obtained silyl compound is shown in FIG. 4, and the IR spectrum is shown in FIG.
Absorption peak in ¹ H-NMR spectrum shown in FIG.

a: 7.49-7.37 ppm (4H),
b: 7.07-6.94 ppm (m 12H),
c: 5.03 ppm (1H),
d: 4.41 ppm (2H)
e: 4.18 ppm (2H),
f: 3.84-3.79 ppm (6H),
g: 3.2-3.17 (2H)
h: 2.31 (6H)
i: 1.61 ppm (2H),
j: 1.24 ppm (9H),
k: 0.65-0.61 ppm (2H)

ポリビニルブチラール １部
テトラヒドロフラン（以後ＴＨＦ） ５０部
の分散液をブレード塗工して０．２μの電荷発生層を設けた。 Example 2
On the aluminum plate, a polyamide layer (Amilan CM8000 manufactured by Toray Industries, Inc.) was provided with a 0.5 μm subbing layer with a methanol solution.
2 parts of the following charge generating materials

Polyvinyl butyral 1 part Tetrahydrofuran (hereinafter THF) 50 parts dispersion was blade coated to provide a 0.2μ charge generation layer.

The following solution was blade coated thereon, dried and cured at 130 ° C. for 30 minutes to provide a 15 μm charge transport layer, and an electrophotographic photosensitive member was obtained.
No. 2 silyl compounds 1 part THF 2 parts dibutyltin diacetate 0.01 part This photoreceptor was rotated 1000 times using an electronic paper analyzer manufactured by Kawaguchi Electric Co., Ltd., charged (Vd) at a discharge current of 20 μA for 20 seconds, and left in the dark for 20 seconds. As a result of measuring the sensitivity (E1 / 2) that is exposed to the light potential (Dd) and white light of 5.3 Lux and becomes a half potential, Vd: 1100 V, Dd: 900 V, E1 / 2: 1.3 lux · sec Met.

Example 3
An undercoat layer and a charge generation layer were provided in the same manner as in Example 2, and the following charge transport layer was provided in the same manner as in Example 2 to obtain an electrophotographic photoreceptor. The obtained photoreceptor was used and evaluated in the same manner as in Example 2.
No. 1 silyl compound 1 part THF 2 parts dibutyltin diacetate 0.01 part Vd: 1000 V, Dd: 950 V, E1 / 2: 1.2 lux · sec

Example 4
An undercoat layer and a charge generation layer were provided in the same manner as in Example 2, and the following charge transport layer was provided in the same manner as in Example 2 to obtain an electrophotographic photoreceptor. The obtained photoreceptor was used and evaluated in the same manner as in Example 2.
No. 7 silyl compounds 1 part THF 2 parts dibutyltin diacetate 0.01 part Vd: 1200 V, Dd: 1050 V, E1 / 2: 1.5 lux · sec

ポリカーボネート（帝人化成社製 Ｋ１３００） １部
ＴＨＦ １３部
Ｖｄ：１１００Ｖ、Ｄｄ：９９０Ｖ、Ｅ１／２：１．１ｌｕｘ・ｓｅｃ Comparative Example 1
An undercoat layer and a charge generation layer were provided in the same manner as in Example 2, and the following charge transport layer was provided in a thickness of 15 μm in the same manner as in Example 2 to obtain an electrophotographic photosensitive member. The obtained photoreceptor was used and evaluated in the same manner as in Example 2.
1 part of the following charge transport materials

Polycarbonate (Teijin Chemicals K1300) 1 part THF 13 parts Vd: 1100 V, Dd: 990 V, E1 / 2: 1.1 lux · sec

実施例２〜４は摩耗量が小さく、比較例１は摩耗量が大きく、実施例は機械的強度が高いことがわかる。 The electrophotographic photoreceptors obtained in Examples 2 to 4 and Comparative Example 1 were subjected to a wear test of 2000 rotations with a wear wheel CS10 using a rotary abrasion tester manufactured by Toyo Seiki Co., Ltd. The amount of wear was expressed as weight loss.

It can be seen that Examples 2 to 4 have a small amount of wear, Comparative Example 1 has a large amount of wear, and Examples have high mechanical strength.

Example 5
The following coating solution was applied to an aluminum cylinder of φ30 mm and L340 mm by a dipping method to obtain an electrophotographic photosensitive member.
The film thickness was 4 μm for the undercoat layer / 0.2 μm for the charge generation layer / 20 μm for the charge transport layer.
[Coating liquid for undercoat layer]
The following composition was prepared by dispersing for 24 hours with a ball mill.
Alkyd resin (Beccosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
6 parts Melamine resin (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
4 parts Titanium oxide (CREL Ishihara Sangyo Co., Ltd.) 40 parts Methyl ethyl ketone 200 parts

ポリビニルブチラール（ＵＣＣ：ＸＹＨＬ） １部
テトラヒドロフラン ５０部 [Coating liquid for charge generation layer]
The following composition was pulverized and dispersed for 72 hours in a Vollimill.
2 parts of the following charge generating materials

Polyvinyl butyral (UCC: XYHL) 1 part Tetrahydrofuran 50 parts

Ｎｏ．１のシリル化合物 １部
テトラヒドロフラン（ＴＨＦ） ２部
ジブチル錫ジアセテート ０．０２部
の溶液を２時間攪拌し、リング塗工し、１３０℃で３０分間乾燥、硬化させ、２０μｍの電荷輸送層を設けた。 [Coating liquid for charge transport layer]
0.5 parts of the following charge transport materials

No. 1 silyl compound 1 part Tetrahydrofuran (THF) 2 parts Dibutyltin diacetate A solution of 0.02 part is stirred for 2 hours, ring coated, dried and cured at 130 ° C. for 30 minutes, and provided with a 20 μm charge transport layer It was.

１％ＴＨＦ溶液のシリコーンオイル（信越化学社製 ＫＦ５０） ０．１部
ＴＨＦ １００部 Example 6
In the same manner as in Example 5, an undercoat layer and a charge generation layer were provided, and the following charge transport layer was provided at 20 μm. Then, the following protective layer coating solution was applied by a spray method and dried and cured at 130 ° C. for 30 minutes. A 5 μm protective layer was provided to obtain an electrophotographic photosensitive member.
[Coating liquid for charge transport layer]
Polystyrene (MW-1 manufactured by Toyo Styrol Co., Ltd.) 10 parts The following charge transport material 10 parts

Silicone oil in 1% THF solution (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 part THF 100 parts

[Protective layer coating solution]
No. 2 silyl compounds 1 part methyltrimethoxysilane 1 part isopropyl alcohol 5 parts THF 5 parts 10% hydrochloric acid aqueous solution 0.1 part

１％ＴＨＦ溶液のシリコーンオイル（信越化学社製 ＫＦ５０） ０．１部
ＴＨＦ １００部 Example 7
In the same manner as in Example 5, an undercoat layer and a charge generation layer were provided, and the following charge transport layer was provided at 20 μm. Then, the following protective layer coating solution was applied by a spray method and dried and cured at 130 ° C. for 30 minutes. A 5 μm protective layer was provided to obtain an electrophotographic photosensitive member.
[Coating liquid for charge transport layer]
Polycarbonate Z (TS-2050 manufactured by Teijin Chemicals Ltd.) 10 parts 10 parts of the following charge transport material

Silicone oil in 1% THF solution (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 part THF 100 parts

[Protective layer coating solution]
No. 9 silyl compounds 1 part Methyltrimethoxysilane 0.6 part Triethoxysilane 0.3 part Trimethylmethoxysilane 0.1 part Isopropyl alcohol 5 parts THF 5 parts 10% aqueous hydrochloric acid 0.1 part

ポリカーボネート樹脂（帝人化成社製 Ｃ−１４００） １部
１％ＴＨＦ溶液のシリコーンオイル（信越化学社製 ＫＦ５０） ０．１部
ＴＨＦ １０部 Comparative Example 2
In the same manner as in Example 5, an undercoat layer and a charge generation layer were provided, and the following charge transport layer 25 μm was provided to obtain an electrophotographic photosensitive member.
[Coating liquid for charge transport layer]
1 part of the following charge transport materials

Polycarbonate resin (Teijin Chemicals C-1400) 1 part Silicone oil in 1% THF solution (KF50, Shin-Etsu Chemical Co., Ltd.) 0.1 part THF 10 parts

Comparative Example 3
An electrophotographic photosensitive member was obtained in the same manner as in Example 6 except that an undercoat layer and a charge generation layer were provided in Example 6, a charge transport layer was provided in a thickness of 25 μm, and a protective layer was not provided.
Comparative Example 4
An electrophotographic photosensitive member was obtained in the same manner as in Example 7 except that the protective layer was not provided in Example 7 and a charge transport layer of 25 μm was provided.

After the electrophotographic photoreceptors of Examples 5 to 7 and Comparative Examples 2 to 4 produced as described above were used for mounting, evaluation was performed as follows.
[Actual machine running characteristics evaluation method]
Using a commercially available electrophotographic copying machine Imagio Neo 270 [manufactured by Ricoh Co., Ltd.], each photoconductor was subjected to a running test up to 10,000 sheets. During and after the test, evaluation of the image quality characteristics and the photosensitive layer abrasion amount of the photoconductor was performed in a timely manner.
Dark potential (VD): The surface potential of each photoconductor was adjusted to an initial value of 850V.
Bright part potential (VL): The surface potential of each photoconductor was adjusted to an initial 80V.
The amount of change in each VD and VL was observed.
Image quality: Overall evaluation such as solid density, fine line reproducibility, abnormal image, etc. Abrasion amount: Amount of decrease in photosensitive layer thickness due to actual machine running These results are shown in Table 2.

Example 8
A subbing layer was provided on a nickel substrate having a diameter of 168 mm and a thickness of 30 μm in the same manner as in Example 5, and the following charge generation layer solution was applied thereon and dried at 80 ° C. to provide a 0.2 μm charge generation layer.
[Coating liquid for charge generation layer]
Oxotitanium phthalocyanine pigment 2 parts Polyvinyl butyral (UCC: XYHL) 0.2 part Tetrahydrofuran 50 parts

ポリカーボネート樹脂（帝人化成社製 ＴＳ−２０５０） １部
テトラヒドロフラン（ＴＨＦ） ２部
１％ＴＨＦ溶液のシリコーンオイル（信越化学社製 ＫＦ５０） ０．１部 Then, the following charge transport layer 20 μm was provided thereon.
[Coating liquid for charge transport layer]
1 part of the following charge transport materials

Polycarbonate resin (TS-2050 manufactured by Teijin Chemicals Ltd.) 1 part Tetrahydrofuran (THF) 2 parts Silicone oil in 1% THF solution (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 part

Next, the following protective layer coating solution was applied on the charge transport layer by a spray method, dried and cured at 130 ° C. for 30 minutes, and a 5 μm protective layer was provided to obtain an electrophotographic photoreceptor.
No. 1 silyl compound 0.9 part Dimethyldimethoxysilane 0.1 part Tetrahydrofuran (THF) 5 part Dibutyltin diacetate 0.02 part Although the substrate of this photoconductor is as thin as 30 μm, deformation due to shrinkage and surface It was clear without cracks.
This photoreceptor was mounted on Ricoh's Imagioneo C270 and a 10,000 sheet passing test was conducted. This apparatus is a belt-like photosensitive member shown in FIG.
As a result, there was no abnormal image and the image was clear even after 10,000 sheets. Further, it was a highly durable photoconductor with no wear, no cracks and no peeling.

  As described above, the silyl compound of the present invention realizes a highly durable photoreceptor excellent in mechanical durability and maintaining high image quality.

1 is a conceptual diagram of an image forming apparatus according to the present invention. It is another conceptual diagram of the image forming apparatus according to the present invention. It is a conceptual diagram of the process cartridge used by this invention. 1 is a ¹ H-NMR spectrum of a silyl compound obtained in Example 1. 2 is an IR spectrum of the silyl compound obtained in Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Charger before transfer 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Charger before cleaning 14 Fur brush 15 Blade 21 Photoconductor 22a , 22b Drive roller 23 Charger 24 Image exposure source 25 Transfer charger 26 Pre-cleaning exposure 27 Cleaning brush 28 Static elimination light source 31 Photoconductor 32 Cleaning blade 33 Charging roller 34 Developing unit 35 Cleaning unit 36 Conveying screw 37 Developer sleeve 38 Developer set case 39 Doctor 40 Toner transport coil 41 Image exposure unit

Claims (9)

A silyl compound represented by the following general formula 1.

{Wherein R ¹ , R ² and R ³ represent an alkoxy group having 1 to ³ carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and the number of alkoxy groups is two or more. Ar ¹ and Ar ² represent the same or different substituted or unsubstituted aryl group, X is a single bond, an oxygen atom, —COO—,

(R ⁴ represents hydrogen, an alkyl group, or an aryl group, a represents an integer of 2 to 4, and b represents 1 or 2), and m and n represent an integer of 1 to 5. } The silyl compound according to claim 1, which is synthesized from an alcohol compound represented by the following general formula 2 and an isocyanate compound represented by the following general formula 3.

{Ar ¹ and Ar ² represent the same or different substituted or unsubstituted aryl groups, and X represents a single bond, an oxygen atom, —COO—,

(R ⁴ represents hydrogen, an alkyl group, or an aryl group, a represents an integer of 2 to 4, and b represents 1 or 2), and m represents an integer of 1 to 5. }

(R ¹ , R ² , R ³ represent an alkoxy group having 1 to ³ carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, the alkoxy group is 2 or more, and n is an integer of 1 to 5 Represents.)   An electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, comprising the silyl compound according to claim 1 or 2 and / or a cured product thereof. 4. The electrophotographic photoreceptor according to claim 3, wherein the cured product is obtained by curing the silyl compound and a compound represented by the following general formula 4.

(R ⁵ , R ⁶ , R ⁷ and R ^{8 each} represent a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group, and at least one is an alkoxy group.)   5. The photosensitive layer according to claim 3, wherein the photosensitive layer is a laminated photosensitive layer in which a charge generation layer and a charge transport layer are stacked, and the charge transport layer contains the silyl compound and / or a cured product thereof. The electrophotographic photosensitive member described.   The electrophotographic photoreceptor according to claim 3 or 4, wherein the electrophotographic photoreceptor has a protective layer on a photosensitive layer, and the protective layer contains the silyl compound and / or a cured product thereof. .   The electrophotographic photosensitive member according to claim 3, wherein the electrophotographic photosensitive member has a belt shape, a sheet shape, or a drum shape.   7. The 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 the electrophotographic photosensitive member according to any one of claims 3 to 6. An image forming apparatus.   7. The electrophotographic photosensitive member according to claim 3 and at least one unit selected from a charging unit, a developing unit, and a cleaning unit are integrally supported, and are detachable from the main body of the image forming apparatus. A process cartridge for an image forming apparatus.

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