JPH1069110A - Electrophotographic photoreceptor, process cartridge with same and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior film forming ability, superior sensitivity and superior durability and to form a high quality image by forming a photosensitive layer contg. a polysilane compd. having a specified constituent unit and a specified group as a terminal group of a polymer chain. SOLUTION: This electrophotographic photoreceptor has a photosensitive layer contg. a polysilane compd. having constituent units represented by the formula and groups selected from among hydroxyl, alkoxy and aryloxy groups as the terminal groups of the polymer chain. In the formula, R1 is H, alkyl or aralkyl and R2 is ethyl, cycloalkyl, vinyl, >=3C alkyl having a prim. or sec. C atom bonding directly to the phenyl group or unsatd. hydrocarbon. The polymer chain may have two or more kinds of constituents units represented by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member using an organic material. More specifically, the present invention relates to an electrophotographic photoreceptor having a photosensitive layer containing a novel polysilane compound that provides improved electrophotographic properties. Further, the present invention relates to a process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Various organic photoconductive polymers such as polyvinyl carbazole have been proposed as organic photoconductive materials for use in electrophotographic photoreceptors. Although these polymers are superior to inorganic photoconductive materials in terms of film-forming properties and lightness, they have not yet obtained sufficient film-forming properties, and are stable in sensitivity, durability and environmental changes. The properties were inferior to those of the inorganic photoconductive materials. As an organic photoconductive material for an electrophotographic photoreceptor, a hydrazone compound according to US Pat. No. 4,150,987 and a triarylpyrazoline compound according to US Pat. Showa 51-94828
And 9-styrylanthracene compounds are proposed in JP-A-51-94829 and are low-molecular-weight compounds. All of these low-molecular organic photoconductive materials are intended to solve the problem of film-forming property which is a problem in the field of organic photoconductive polymers by properly selecting a binder to be used. However, it was not enough in terms of sensitivity. In recent years, in order to improve sensitivity to incident light, charge holding power, surface strength, and the like, an electrophotographic photosensitive member having a laminated structure in which a photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has been disclosed in, for example, US Pat. 3,837,851 and 3,871,851
No. 882.

However, when the charge transport layer is formed using a conventional low molecular organic photoconductive material, the organic photoconductive material is used in any case by being mixed with a predetermined binder resin. For this reason, the obtained electrophotographic photoreceptor had low charge mobility and was not always sufficient in sensitivity and characteristics due to the binder resin.

[0004] For these reasons, polysilanes have attracted attention as photoconductive materials that have the potential to provide desired organic electrophotographic photoreceptors.

Examples of using polysilane as a photoconductor are described in US Pat. No. 4,618,551, US Pat. No. 4,772,525, and JP-A-62-26996.
No. 4, JP-A-3-198061, and the like.

According to US Pat. No. 4,618,551, a polysilane compound is applied to an electrophotographic photoreceptor. However, the absolute value of the surface potential used in a normal copying machine is 400 to 800 V. On the other hand, it is used at a high potential of 1000V. This is presumably to eliminate spot-like image abnormalities due to polysilane structural defects. Japanese Patent Application Laid-Open No. 62-269964 discloses an electrophotographic photoreceptor using a polysilane compound, but has a low photosensitivity and has no advantage over a conventional photoreceptor. JP-A-3-19
No. 8061 discloses that a photosensitive layer having excellent flexibility, film strength, and adhesiveness can be obtained by including a polysilane having a substituted or unsubstituted arylene group in a main chain in a photosensitive layer. However, the introduction of carbon atoms into the main chain of polysilane sacrifices the inherent high mobility of polysilane.

[0007]

As a result of a detailed study of the structure and electrophotographic properties of polysilane, it was found that the para-substituent of the phenyl group bonded to polysilane had electrophotographic properties,
The present inventors have found that they greatly contribute to the film forming property, the mechanical strength of the film, and the image characteristics, and have reached the present invention.

A main object of the present invention is to provide an electrophotographic photosensitive member having a photosensitive layer containing an organic photoconductive material, which satisfies various requirements required for the electrophotographic photosensitive member.

Another object of the present invention is to provide an electrophotographic photosensitive member having particularly excellent sensitivity and durability.

It is still another object of the present invention to provide an electrophotographic photosensitive member having excellent film forming ability.

Still another object of the present invention is to provide an electrophotographic photosensitive member having particularly excellent image characteristics.

Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

[0013]

That is, the present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer has the following formula (1):

[0014]

[Outside 7] (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
It shows a group selected from the group consisting of the above alkyl groups and unsaturated hydrocarbon groups. An electrophotographic photoreceptor comprising a polysilane compound having a structural unit represented by the formula (I) and having a group selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group as a terminal group of a polymer chain. .

Further, the present invention is a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[0016]

DETAILED DESCRIPTION OF THE INVENTION In the formula (1), R ₁ is selected from the group consisting of a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and an aralkyl group such as a benzyl group and a phenethyl group. R ₂ is an ethyl group,
It is selected from the group consisting of a cycloalkyl group, a vinyl group, an alkyl group having 3 or more carbon atoms in which the carbon atom directly bonded to the benzene ring in the formula is a primary carbon or a secondary carbon, and an unsaturated hydrocarbon group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclohexyl group, and a cyclopentyl group. In the formula, the carbon atom directly bonded to the phenyl group is a primary carbon or a secondary carbon, and an alkyl group having 3 or more carbon atoms and an unsaturated group. As the hydrocarbon group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, isopentyl group, neopentyl group, allyl group,
Examples thereof include a 1-propenyl group and a 2-methylallyl group.

The terminal group of the polymer chain is selected from the group consisting of a hydroxyl group, a methoxy group, an ethoxy group, an alkoxy group such as a propoxy group and a butoxy group, and an aryloxy group such as a phenoxy group and a naphthyloxy group.

The alkyl group, aralkyl group, cycloalkyl group, vinyl group, and the above-mentioned R ₁ , R ₂ and terminal groups
The unsaturated hydrocarbon group, the alkoxy group and the aryloxy group may have a substituent, and the substituent includes an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a phenyl group and a naphthyl group. Aralkyl groups such as aryl groups, benzyl groups and phenethyl groups, methoxy groups,
Examples include a group selected from an alkoxy group such as an ethoxy group, a propoxy group and a butoxy group, and a silyl group such as a trimethylsilyl group and a triphenylsilyl group.

In the present invention, the polymer chain may have two or more types of structural units represented by the formula (1). It may have a structural unit.

The polysilane compound of the present invention has the following formula (2)
It is preferable to be represented by

[0021]

[Outside 8] (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
R ₃ and R ₄ represent a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkoxy group, and n and m Represents the ratio of monomer units in the polymer chain, n ≠ 0, the sum of n + m is 1, and A and A ′ represent groups selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. )

In the formula (2), R ₁ and R ₂ are the same as described above, and R ₃ and R ₄ are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, phenyl group and naphthyl group. It is selected from the group consisting of aralkyl groups such as aryl group, benzyl group and phenethyl group, and alkoxy groups such as methoxy group and ethoxy group.

N and m represent the proportion of monomer units in the polymer chain, where n ≠ 0 and the sum of n + m is 1.
In the present invention, n is preferably 0.1 or more. In addition, these units may be arranged in the order shown in Expression (2), or the units may be arranged alternately or at random. Further, each of R _{1 to} R ₄ may have two or more types.

A and A 'are alkoxy groups such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group;
And aryloxy groups such as phenoxy and naphthyloxy groups.

The alkyl group, aryl group, aralkyl group, cycloalkyl group, R _{1 to} R ₄ , A and A ′,
The vinyl group, the unsaturated hydrocarbon group, the alkoxy group and the aryloxy group may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an alkyl group such as a propyl group and a butyl group, a phenyl group and a naphthyl group. An aryl group such as a group,
It is selected from aralkyl groups such as benzyl group and phenethyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, and silyl groups such as trimethylsilyl group and triphenylsilyl group.

In the present invention, it is preferable that R ₁ is an alkyl group and R ₂ is an ethyl group from the viewpoint that excellent electrophotographic characteristics can be obtained and the compound can be synthesized at low cost.

Preferred specific examples of the polysilane compound of the present invention are shown in Tables 1 to 3.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

(Production Example) As a method for producing the above-mentioned polysilane, a known production method (Wurtz method or electrode reduction method) can be used.

The production method by the Wurtz method is disclosed in
As cited in JP-A-70749, it can be obtained by adding toluene as a solvent to various starting dichlorosilanes and performing a dechlorination-condensation reaction with sodium at 95 to 120 ° C. Further, as a general example of the production method by the electrode reduction method, a journal of chemical society chemical communication (J. Ch.
em. Soc. Chem. Commun. , 1160
(1990)). That is, it can be produced by adding tetrahydrofuran as a solvent to various kinds of dichlorosilane as a starting material, and performing reduction with a Mg electrode using lithium perchlorate as a supporting electrolyte.

The polysilane of the present invention produced by the above-mentioned production method can have a weight average molecular weight (Mw) of 6,000 to 2,000,000, depending on the production conditions.

The electrophotographic photoreceptor of the present invention basically comprises
It comprises a support and a photosensitive layer containing the above-mentioned polysilane compound provided on the support.

Even if the photosensitive layer is composed of a single layer,
Alternatively, the photosensitive layer may be composed of a plurality of layers having different functions, but in the present invention, the photosensitive layer is preferably composed of a plurality of layers.

FIG. 1 schematically shows an example of the electrophotographic photosensitive member of the present invention in which the photosensitive layer is a single layer. In FIG. 1, 101 is a support, and 102 is a photosensitive layer containing the above-mentioned polysilane compound. In this case, the photosensitive layer 102 is a photosensitive layer containing the above-mentioned polysilane compound, that is, a substance capable of transporting electric charges (charge transporting substance) and a substance capable of generating electric charges (charge generating substance). . The electrophotographic photoreceptor of FIG. 1 may have an undercoat layer (not shown) having a barrier function and an adhesive function between the support and the photosensitive layer, if necessary. A surface protective layer (not shown) for protecting the photosensitive layer may be provided on the photosensitive layer.

In the photosensitive layer shown in FIG. 1, the weight ratio of the charge generating substance to the charge transporting substance (the above-mentioned polysilane compound) (charge generating substance: charge transporting substance) is preferably from 1: 100 to 1: 1. Especially 1:20 to 1:
3, and it is preferable that both substances are contained in a state in which they are uniformly present in the layer. Further, the layer thickness is preferably 4 to 40 μm, particularly preferably 7 to 30 μm.

As the charge generating substance, a known organic charge generating substance or a known inorganic charge generating substance can be selectively used. Examples of such organic charge generating substances include, for example,
Examples include azo pigments, phthalocyanine pigments, anthrone pigments, quinone pigments, pyrazolone pigments, indigo pigments, quinacridone pigments, and pyrylium dyes. In addition, examples of the inorganic charge generating substance include selenium, selenium-tellurium, selenium-arsenic, and the like.

FIG. 1 can be formed, for example, as follows. That is, first, a predetermined amount of the above-described charge generating substance is dispersed in an appropriate solvent, and a predetermined amount of a polysilane compound is dissolved in the obtained suspension to prepare a coating liquid. The obtained coating liquid is coated on the surface of the support by an appropriate coating means so that the layer thickness after drying is in the above-mentioned predetermined thickness range, and the formed liquid coat is dried and solidified by known means. I do. Examples of the solvent used at this time include aromatic solvents such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, dichloroethane, and chloroform, and tetrahydrofuran and dioxane.

Examples of the coating means include a wire bar method, a dipping method, a doctor blade method, a spray method, a roll method, a bead method, and a spin coating method.

When the above-described undercoat layer is provided on the electrophotographic photosensitive member of FIG. 1, the layer thickness is preferably from 0.1 to 5 μm, particularly preferably from 0.1 to 3 μm.

The subbing layer is suitably selected from the group consisting of casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon and alkoxymethylated nylon), polyurethane and aluminum oxide. It is composed of the following materials. When the undercoat layer material to be used is soluble in a solvent, the undercoat layer may be dissolved in a suitable solvent,
When the material is insoluble in a solvent, it is dispersed in a binder resin solution, and the obtained coating solution is coated on the surface of the support 101 in the same manner as in the case of the photosensitive layer described above. Is formed by drying and solidifying the formed liquid coat.

In the case where the above-mentioned surface protective layer is provided on the electrophotographic photosensitive member of FIG. 1, the desirable layer thickness is in the range of 0.1 to 5 μm. The surface protective layer is made of a resin such as polycarbonate A, polycarbonate Z, polyarylate, polyester, and polymethyl acrylate. The surface protective layer may contain additives such as a resistance adjusting agent and a deterioration inhibitor.

The surface protective layer is prepared by dissolving the resin in an appropriate solvent and coating the obtained coating liquid on the surface of the previously formed photosensitive layer in the same manner as in the case of the above-mentioned photosensitive layer. Is formed by drying and solidifying the formed liquid coat.

When the above-mentioned resistance adjusting agent, deterioration preventing agent and the like are contained in the surface protective layer, the additives may be uniformly dispersed in the coating liquid for the surface protective layer.

The electrophotographic photoreceptor of the present invention has a photosensitive layer having a plurality of functionally separated layers.
Shown in That is, the electrophotographic photosensitive member of FIG.
A charge generation layer 202 containing a charge generation substance and a charge transport layer 203 containing the above-mentioned polysilane compound are provided in this order from the support 201 side. Also,
The electrophotographic photoreceptor of the present invention in the form shown in FIG.
01, a charge transport layer 302 containing the above-mentioned polysilane compound and a charge generation layer 303 containing a charge generating substance.
From the support 301 side in this order.

As in the case of the electrophotographic photosensitive member of FIG. 1, both the electrophotographic photosensitive members of FIGS. 2 and 3 may have an undercoat layer (not shown) and / or a surface protective layer, if necessary. (Not shown).

That is, the undercoat layer is provided between the support 201 and the charge generation layer 202 in the case of the electrophotographic photosensitive member shown in FIG.
1 and the charge transport layer 302.

The surface protective layer is provided on the charge transport layer 203 in the case of the electrophotographic photosensitive member shown in FIG. 2, and is provided on the charge generating layer 303 in the case of the electrophotographic photosensitive member shown in FIG.

The thickness of the charge generation layer 202 shown in FIG.
To 5 μm, particularly preferably 0.05 to 2 μm, and the thickness of the charge transport layer 203 is preferably 4 to 50 μm, and particularly preferably 7 to 30 μm.

The charge transport layer 302 shown in FIG.
To 50 μm, particularly preferably 7 to 30 μm.
μm, and the thickness of the charge generation layer 303 is preferably 1 to 15 μm, and more preferably 3 to 1 μm.
It is preferably 0 μm.

When an undercoat layer is provided on the electrophotographic photosensitive member shown in FIG. 2 or FIG.
It is 1 to 5 μm, more preferably 0.1 to 3 μm. Similarly, when a surface protective layer is provided, the layer thickness is preferably 0.1 to 5 μm.

As the charge generation material contained in the charge generation layer 202 or 303, a known organic charge generation material or a known inorganic charge generation material can be used. Specific examples of such organic charge generating substances include, for example, azo pigments, phthalocyanine pigments, anthantrone pigments, quinone pigments, pyranthrone pigments, indigo pigments, quinacridone pigments, and pyrylium pigments. Similarly, specific examples of the inorganic charge generating substance include selenium, selenium-tellurium, selenium-arsenic, and the like.

The charge generation layer 202 or 303 can be formed by a method of depositing the charge generation material by a known means or a method of preparing a coating solution containing the charge generation material, applying the coating solution, and drying and solidifying the coating solution. Can be formed. Of these two methods, the latter method is more preferable. That is, according to the latter method, the dispersed state of the charge generating substance in the formed charge generating layer can be easily controlled. Specifically, using a suitable dispersion medium, together with this, the charge generating substance is introduced into a suitable solvent to prepare a coating liquid in which the charge generating substance is uniformly dispersed, and this is applied. A charge generation layer is formed by forming a liquid coat and drying and solidifying the liquid coat.

Preferred examples of the dispersion medium include a so-called binder resin such as an insulating resin and an organic photoconductive polymer. As specific examples of such a binder resin, polyvinyl butyral, polyvinyl benzal,
Examples thereof include polyarylate, polycarbonate, polyester, phenoxy resin, cellulosic resin, acrylic resin, and polyurethane. In addition to the above, if necessary, the above-mentioned polysilane compound used in the present invention can be used as the dispersion medium. In any case, the amount of the dispersion medium to be used is preferably 80% by weight or less, more preferably 80% by weight or less, in terms of the content (weight ratio) in the finally formed charge generation layer (202 or 203). Is 40% by weight or less.

As the solvent, any solvent may be used as long as it dissolves the above-mentioned binder resin and allows the above-mentioned charge generating substance to be uniformly dispersed in the dissolved binder resin. Specific examples of such a solvent include, for example, ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as cyclohexanone and methyl ethyl ketone; amides such as N, N-dimethylformamide; esters such as methyl acetate and ethyl acetate: Aromatics such as toluene, xylene and chlorobenzene: alcohols such as methanol, ethanol and 2-propanol: aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride and trichloroethylene, etc. Can be

As a method of forming the liquid coat by applying the above-mentioned coating liquid, a known appropriate coating method can be adopted. Examples of such a coating method include a wire bar coating method, a dipping method, a doctor blade method, a spray method, a roll method, a bead method, and a spin coating method.

For drying and solidifying the formed liquid coat, a drying and solidifying method that does not damage the formed charge generation layer (202 or 303), such as a known air drying method, can be adopted.

The charge transport layer 203 or 302 containing the above-mentioned polysilane compound is used as the charge generation layer (202).
Or 303) can be formed in the same manner as in the case of formation. That is, the charge transport layer is prepared by dissolving the above-mentioned polysilane compound in a solvent preferably in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight, based on the solvent to prepare a coating solution. It can be formed by coating to form a liquid coat, and drying and solidifying the liquid coat.

Examples of the solvent include aromatic solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, dichloroethane and chloroform, tetrahydrofuran and dioxane. The application of the coating liquid and the drying and solidification of the liquid coat can be performed in the same manner as in the formation of the charge generation layer (202 or 303).

When an undercoat layer and / or a surface protective layer are provided on the electrophotographic photosensitive member of FIG. 2 or FIG. 3, any of those layers is the same as that of the electrophotographic photosensitive member of FIG. Can be formed.

The support of the electrophotographic photosensitive member of the present invention (10
1,201,301) are those having conductivity.
Any one may be used. First, for the shape, cylindrical,
Any shape such as a belt shape and a plate shape can be used.
Next, the constituent material may be a member that is entirely conductive, or a member in which the base is an insulating member and the surface on which the photosensitive layer is provided is subjected to a conductive treatment.
Specific examples of the former case include, for example, metal members such as aluminum, copper and zinc, and alloys such as aluminum alloy and stainless steel. For the latter case, polyethylene, polypropylene, polyvinyl chloride,
A member obtained by forming a coating of the above-described metal on a surface of a plastic base member such as polyethylene terephthalate and an acrylic resin by a known vacuum deposition method, and a conductive material such as titanium oxide, tin oxide, carbon black, and silver is formed on the surface of the plastic base member. And a member in which the conductive particles are impregnated into an impregnable base member such as paper and plastic, for example. In addition to these members, a member in which the surface of a suitable metal base member is coated with the conductive particles using a suitable binder resin can also be used as the conductive support.

In any of the electrophotographic photosensitive members shown in FIGS. 1 to 3 described above, when the next constituent layer is formed on the previously formed constituent layer, the constituent layer formed first It is preferable to select and use a solvent that does not dissolve.

In the present invention, a known charge transporting material may coexist in the charge transporting layer 203 or 302 containing the above-mentioned polysilane compound. That is, a known charge transporting substance such as a pyrazoline compound, a hydrazone compound, a polyvinyl carbazole compound, a styryl compound, a triarylamine compound, or the like can be mixed with a polysilane compound at an arbitrary ratio to form a charge transporting layer.

FIG. 4 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 rotates during the rotation process.
The peripheral surface is uniformly charged with a predetermined positive or negative potential by the primary charging means 3, and then receives image exposure light 4 from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then developed.
The toner-developed image developed by the toner image is transferred from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed to a transfer material 7 fed therefrom. The image is sequentially transferred by the transfer unit 6.

The transfer material 7 having undergone the image transfer is separated from the surface of the photoreceptor, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy out of the apparatus.

The surface of the photoreceptor 1 after the image is transferred is cleaned by removing the untransferred toner by the cleaning means 9, and is further cleaned by a pre-exposure light 10 from a pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, of the above-mentioned components such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9, a plurality of components are integrally connected as a process cartridge. This process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, which can be attached to and detached from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. Process cartridge 1
It can be 1.

When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is reflected or transmitted from the original, or the original is read by a sensor and is converted into a signal. Laser beam scanning,
Light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.

The electrophotographic photoreceptor of the present invention described above comprises:
The present invention can be applied not only to various electrophotographic copying machines but also to laser beam printers, CRT printers, LED printers, liquid crystal printers, laser plate making, and facsimile outputs.

Hereinafter, the present invention will be further described with reference to examples.
The present invention is not limited by these examples.

Example 1 An electrophotographic photosensitive member of the type shown in FIG. 2 was produced.

An aluminum substrate having a size of 10 cm × 10 cm and a thickness of 50 μm was used as the support 201.

First, a charge generation layer 202 was formed on the surface of the aluminum substrate as follows. That is, 10 parts by weight of oxytitanium phthalocyanine and 5 parts by weight of polyvinyl butyral were dispersed in 90 parts by weight of methyl ethyl ketone using a ball mill to prepare a coating liquid for the charge generation layer 202, and the obtained coating liquid was obtained. Was applied to the surface of the aluminum substrate with a wire bar having a thickness of 0.3 μm after drying to form a liquid coat, followed by drying to form a 0.3 μm thick charge generation layer 202.

Next, Compound No. 25 parts by weight of the polysilane compound No. 8 was dissolved in 75 parts by weight of toluene to prepare a coating liquid for the charge transport layer 203. On the surface of the charge generation layer 202 formed earlier, the obtained coating liquid was dried to a thickness of 20 μm.
The liquid transport coat was formed by coating with a wire bar, and dried to form a charge transport layer 203 having a thickness of 20 μm.

The obtained electrophotographic photosensitive member (sample No. 1)
Was evaluated from various viewpoints.

First, the state of the coating film of the obtained electrophotographic photosensitive member was visually observed.

Next, the electrophotographic photosensitive member was corona-charged at −5 KV in a static manner using an electrostatic copying paper tester Model SP-428 manufactured by Kawaguchi Electric Co., Ltd., and was held for 1 second in a dark place. Exposure is performed at an illuminance of 2.5 lux, and the light sensitivity is examined.
To remove electricity.

Regarding the charging characteristics, the exposure amount (E ₁ ) necessary to attenuate the potential (V ₁ ) one second after corona charging to one half was reduced.
) Was measured.

Further, the residual potential V _SL after the strong exposure was measured, and
The initial residual potential was V ⁰ _SL .

Further, the electrophotographic photosensitive member was attached to a photosensitive member cylinder of a laser beam printer LBP-450 manufactured by Canon Inc., set on the laser beam printer and printed, and an initial image was formed. It was evaluated visually. Then, 3,000 prints were continuously performed, and the images after the 3,000 prints were visually evaluated.

Further, the electrophotographic photosensitive member after the printing of 3,000 sheets was taken out of the laser beam printer, and the electrostatic copying paper test apparatus Model SP-42 was used.
8 examined set to charging characteristics, variation of residual potential (V _SL) to ([Delta] V _SL) was measured.

Table 4 shows the obtained evaluation results.

Examples 2 to 52 Polysilane compound Nos. Electrophotographic photoreceptors were prepared in the same manner as in Example 1 except that polysilane compounds shown in Table 4 were used in place of Sample No. 8.
2).

Each of the obtained photoreceptors was evaluated in the same manner as in Example 1.

Table 4 shows the evaluation results.

Comparative Example 1 Polysilane compound no. In place of 8, the following polysilane compound (D-1) (a is an integer; Mw = 100,000)

[0090]

[Outside 9] An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that Sample No. was used (Sample No. E-1).

The obtained photoreceptor was evaluated in the same manner as in Example 1.

Table 4 shows the results of the evaluation.

Comparative Example 2 The procedure up to the formation of the charge generation layer 202 was performed in the same manner as in Example 1.

Next, the following polysilane compound (D-2)
(B is an integer. Mw = 80,000)

[0095]

[Outside 10] 25 parts by weight were dissolved in 75 parts by weight of toluene to prepare a coating solution for the charge transport layer 203, and the coating solution was applied on the surface of the previously formed charge generating layer 202 in an amount such that the film thickness after drying was 20 μm. As a result, a liquid coat was formed and dried, and the surface became yellow-skinned.

The obtained photoreceptor (sample No. E-2) was evaluated in the same manner as in Example 1.

Table 4 shows the evaluation results.

Comparative Examples 3 and 4 Polysilane compound no. In place of 8, the following polysilane compounds (D-3 and D-4) (c and d are integers; Mw = 15)
(0000 and 100,000)

[0099]

[Outside 11] Were used in the same manner as in Example 1 to prepare two types of electrophotographic photosensitive members (Samples No. E-3 and No. E-4).

The obtained photoreceptor was evaluated in the same manner as in Example 1.

Table 4 shows the results of the evaluation.

Examples 53 to 56 Electrophotographic photosensitive members of the type shown in FIG. 3 were prepared.

As the support 301, 10 cm × 10 cm
A 50 μm-thick aluminum substrate was used.

First, a charge transport layer 302 was formed on the surface of the aluminum substrate. That is, Compound No. 35,3
25 parts by weight of 6, 46 and 52 polysilane compounds
A coating solution for the charge transport layer 302 is prepared by dissolving in a weight part of toluene, and the obtained coating solution is applied on the surface of the aluminum substrate with a wire bar having a thickness of 20 μm after drying to form a liquid coat. Then, the resultant was dried to form a charge transport layer 302 having a thickness of 20 μm.

Next, 5 parts by weight of chloroaluminum phthalocyanine and 25 parts by weight of a polycarbonate resin were dispersed in 70 parts by weight of toluene using a ball mill to prepare a coating liquid for forming the charge generation layer 303, and the obtained coating liquid was obtained. Is formed on the surface of the charge transport layer 302 previously formed to a thickness of 3 μm after drying.
A liquid coat was formed by coating with a wire bar and dried to form a charge generation layer 303 having a thickness of 3 μm (Sample Nos. 53 to 56).

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. However, the polarity of the primary charging was made positive.

Table 4 shows the results of the evaluation.

Comparative Examples 5 to 8 An electrophotographic photoreceptor (Sample Nos. E-5 to E) was prepared in the same manner as in Example 53 except that the polysilane compounds (Nos. D-1 to D-4) used in Comparative Examples 1 to 4 were used instead of 35. -8).

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 53.

Table 4 shows the results of the evaluation.

Comparative Example 9 Polysilane compound no. In place of 35, the following polysilane compound (D-5) (e is an integer. Mw = 50,000)

[0112]

[Outside 12] An electrophotographic photoreceptor (Sample No. E-9) was produced in the same manner as in Example 53, except that Sample No. was used.

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 53.

Table 4 shows the results of the evaluation.

Examples 57 to 65 Electrophotographic photosensitive members of the type shown in FIG. 1 were produced.

As the support 101, 10 cm × 10 cm
A 50 μm-thick aluminum substrate was used.

The photosensitive layer 102 was formed as follows.
That is, 5 parts by weight of X-type metal-free phthalocyanine and Compound No. 20 parts by weight of the polysilane compounds 30, 48, 49 and 53 to 58 were dispersed in 75 parts by weight of toluene using a ball mill to prepare a coating solution for the photosensitive layer 102. The resulting coating solution was applied to the aluminum substrate surface with a wire bar having a thickness of 18 μm after drying to form a liquid coat, and then dried to form a photosensitive layer 102 having a thickness of 18 μm.

The obtained electrophotographic photosensitive member (sample No. 57)
To 65) were evaluated in the same manner as in Example 1.

Table 4 shows the results of the evaluation.

Comparative Example 10 Polysilane compound no. The following polysilane compound (D-6) was substituted for 30 (f is an integer; Mw = 50,000).

[0121]

[Outside 13] An electrophotographic photoreceptor (Sample No. E-10) was produced in the same manner as in Example 57, except for using.

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 57.

The evaluation results are shown in Table 4.

[0124]

[Table 4]

[0125]

[Table 5]

[0126]

[Table 6]

[0127]

As described above, according to the present invention, excellent film-forming ability, excellent sensitivity and excellent durability can be obtained.
An electrophotographic photosensitive member capable of forming a high-quality image, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an electrophotographic photosensitive member of the present invention having a single photosensitive layer.

FIG. 2 is a schematic cross-sectional view of an electrophotographic photosensitive member of the present invention having a photosensitive layer composed of a plurality of layers.

FIG. 3 is a schematic sectional view of an electrophotographic photoreceptor of the present invention having a photosensitive layer composed of a plurality of layers.

FIG. 4 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member according to the present invention.

Claims (12)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer has the following formula (1). (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
It shows a group selected from the group consisting of the above alkyl groups and unsaturated hydrocarbon groups. An electrophotographic photoreceptor comprising a polysilane compound having a structural unit represented by the formula (1) and having, as a terminal group of a polymer chain, a group selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. 2. The polysilane compound is represented by the following formula (2): (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
R ₃ and R ₄ represent a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkoxy group, and n and m Represents the ratio of monomer units in the polymer chain, n ≠ 0, the sum of n + m is 1, and A and A ′ represent groups selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. 2. The electrophotographic photoreceptor according to claim 1, wherein 3. The electrophotographic photoreceptor according to claim 1, wherein R ₁ is an alkyl group and R ₂ is an ethyl group. 4. The electrophotographic photoconductor according to claim 1, wherein the photosensitive layer has a charge generation layer and a charge transport layer, and the charge transport layer contains the polysilane compound. 5. A process cartridge which integrally supports an electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means and is detachable from an electrophotographic apparatus main body. The photoreceptor has a photosensitive layer on a support, and the photosensitive layer has the following formula (1). (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
It shows a group selected from the group consisting of the above alkyl groups and unsaturated hydrocarbon groups. A) a process cartridge comprising a polysilane compound having a structural unit represented by the formula (1) and having, as a terminal group of the polymer chain, a group selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. 6. The polysilane compound represented by the following formula (2): (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
R ₃ and R ₄ represent a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkoxy group, and n and m Represents the ratio of monomer units in the polymer chain, n ≠ 0, the sum of n + m is 1, and A and A ′ represent groups selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. 6. The process cartridge according to claim 5, wherein 7. The process cartridge according to claim 5, wherein R ₁ is an alkyl group and R ₂ is an ethyl group. 8. The process cartridge according to claim 5, wherein the photosensitive layer has a charge generation layer and a charge transport layer, and the charge transport layer contains the polysilane compound. 9. An electrophotographic photoreceptor, charging means, exposure means,
In an electrophotographic apparatus having a developing unit and a transfer unit, the electrophotographic photosensitive member has a photosensitive layer on a support, and the photosensitive layer has the following formula (1). (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
It shows a group selected from the group consisting of the above alkyl groups and unsaturated hydrocarbon groups. An electrophotographic apparatus comprising: a polysilane compound having a structural unit represented by the formula (1) and having, as a terminal group of a polymer chain, a group selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. 10. A polysilane compound represented by the following formula (2): (In the formula, R ₁ represents a group selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group, and R ₂ represents a carbon atom directly bonded to an ethyl group, a cycloalkyl group, a vinyl group, and a phenyl group. Carbon number 3 which is carbon or secondary carbon
R ₃ and R ₄ represent a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkoxy group, and n and m Represents the ratio of monomer units in the polymer chain, n ≠ 0, the sum of n + m is 1, and A and A ′ represent groups selected from the group consisting of a hydroxyl group, an alkoxy group and an aryloxy group. 10. The electrophotographic apparatus according to claim 9, wherein 11. The electrophotographic apparatus according to claim 9, wherein R ₁ is an alkyl group and R ₂ is an ethyl group. 12. The electrophotographic apparatus according to claim 9, wherein the photosensitive layer has a charge generation layer and a charge transport layer, and the charge transport layer contains the polysilane compound.