JP2579545B2 - Electrophotographic photoreceptor having photoreceptive layer containing polysilane compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor using an organic material. More specifically, the present invention relates to an electrophotographic photoreceptor having a photoreceptive layer formed using a novel polysilane compound that provides improved electrophotographic properties.

[Description of Prior Art]

Conventionally, as an organic photoconductive material used for an electrophotographic photoreceptor, various organic photoconductive polymers including polyvinyl carbazole have been proposed. Despite their superiority in film-forming properties and lightness compared to inorganic photoconductive materials, these polymers have been difficult to put to practical use until today because they still have sufficient film-forming properties. This is because they are inferior to inorganic photoconductive materials in sensitivity, durability and stability against environmental changes. In addition, as an organic photoconductive material for an electrophotographic photoreceptor, U.S. Pat.
No. 987 describes hydrazone compounds as disclosed in U.S. Pat.
No. 37,851 proposes a triarylpyrazoline compound, and JP-A-51-94828 or JP-A-51-94829 proposes a 9-styrylanthracene compound, respectively, which are of low molecular weight. However, all of these low-molecular organic photoconductive materials do not solve the problem of the film forming property which is a problem in the field of organic photoconductive polymers by properly selecting the binder to be used. Although there is not enough in terms of sensitivity,
It is not practical to obtain a desired electrophotographic photoreceptor.

For these reasons, a laminated structure in which a photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has recently been proposed.
An electrophotographic photoreceptor having this laminated structure as a photosensitive layer can be improved in terms of sensitivity to visible light, charge retention, surface strength, and the like. Such electrophotographic photoreceptors are described, for example, in U.S. Patent Nos. 3,837,851 and 3,837,851.
It is disclosed in the specification of 71,882 and the like.

However, when producing the charge transport 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 has low charge mobility, sensitivity and characteristics are not always sufficient due to the binder resin, and when a repetitive charging and exposure is performed, a bright portion potential and a dark portion potential are reduced. Fluctuations are large, resulting in insufficient durability.

For these reasons, polysilane has attracted attention as a photoconductive material that may provide a desired organic electrophotographic photoreceptor.

By the way, it has been reported that so-called polysilanes are insoluble in solvents, but the [The Journal of American Chemical Society (The Journa
l of American Chemical Society) 125 , 2291pp (192
4)], and in recent years, it has been reported that polysilane is soluble and soluble and can form a film. [The Journal of American Ceramic Society 6
1 , 504pp (1978)].

In addition, it has been reported that polysilane has the property of an optical semiconductor capable of transferring charges by a σ-bond of the main chain [Physical Review (Physical Revie).
w), B 35 , 2818 pp (1987)].

For these reasons, application of polysilane to photoconductors for electrophotography is expected.However, in order to obtain desired electrophotographic photoconductors that can be practically used by using polysilane as a photoconductive material, the following polysilanes are used. It is required to satisfy at least such requirements. That is, those requirements are: (i) not only solvent-soluble and film-forming ability, but also formation of a film without fine defects and formation of a film with high homogeneity are possible; (ii) electrophotography Since fine defects are not allowed in the photoreceptor, the structure of the substituent is clear and the photoreceptor must be of high quality which does not cause an abnormality in film formation.

Although some reports have been made on the synthesis of polysilanes, none of the reported polysilanes is sufficient for use in electrophotographic photoreceptors. That is, low-molecular-weight polysilanes having a structure in which all Si groups are substituted with organic groups have been reported or proposed [The Journal of American Chemical Society (Journal of American Chemical Society)].
Society), Vol.94, No.11, 3806pp (1972)], Tokubo Sho63
−38033].

The former publication has a structure in which a terminal group of dimethylsilane is substituted with a methyl group, and the latter publication has a structure in which a terminal group of dimethylsilane is substituted with an alkoxy group. However, all have a degree of polymerization of 2
6, which does not exhibit the characteristics of a polymer. That is, because of its low molecular weight, it has no film forming ability as it is, and is difficult to use industrially. A structure in which all Si groups are replaced by organic groups with high molecular weight polysilane has recently been reported [Nikkei New Materials, August 15, Issue 46, p. 46 (1988)], but because of a special reaction intermediate. In addition, the synthesis yield is expected to decrease, and industrial mass production is difficult.

In addition to the above reports, a method for synthesizing polysilane has been reported [The Journal of Organometallic.
Chemistry (The Journal of Organometallic Chemis
try), 198ppC27 (1980), or The Journal of Polymer Science, Polymer Chemistry.
Edition (The Journal of Polymer Science, Polym
er Chemistry Edition), Vol.22 159-170pp (1984)
reference〕.

However, in any of the reported synthesis methods, only the condensation reaction of the polysilane main chain is performed, and there is no mention of a terminal group. In any of the synthesis methods, unreacted chloro groups and by-products are produced by side reactions, and it is difficult to constantly obtain a desired polysilane compound.

There are some examples of using the above polysilane as a photoconductor (U.S. Pat. Nos. 4,861,551 and 4,725,525).
It is considered that there is an effect of unreacted chloro group and by-products due to side reactions.

That is, according to U.S. Pat.No. 4,861,551, the polysilane compound is applied to an electrophotographic photoreceptor,
Image formation by the electrophotographic photoreceptor, whereas the absolute value of the surface potential may be 500 to 800 V in the case of a general copying machine,
The measurement is performed at a surface potential having an abnormally large absolute value, that is, -1000 V. This is because in order to eliminate the problem of causing an electrophotographic photoreceptor to have a defect due to a structural defect of polysilane at a potential having an absolute value of a normal value and causing a spot-like abnormal phenomenon in an obtained image. Conceivable. According to JP-A-62-269964, an electrophotographic photoreceptor is prepared using the above-mentioned polysilane compound, and the photosensitivity is measured. It is understood that it has no advantage over the body or the organic photoreceptor.

As described above, conventional polysilanes have many problems and cannot be used industrially in order to utilize them as electronic materials.

[Object of the invention]

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

Another object of the present invention is particularly excellent in sensitivity and durability,
An object of the present invention is to provide an electrophotographic photoreceptor having a light receiving layer formed by using a novel specific polysilane compound.

Still another object of the present invention is to provide an electrophotographic photoreceptor having a light-receiving layer formed by using a novel specific polysilane compound having good solubility in a solvent and excellent film-forming ability. It is in.

[Structure and effect of the invention]

The present invention achieves the above object, and an electrophotographic photoreceptor provided by the present invention comprises a polysilane compound represented by the following general formula (I) and having a weight average molecular weight of 6000 to 200,000. It is characterized by having a light-receiving layer formed by use.

Wherein R ₁ is an alkyl group having 1 or 2 carbon atoms, R ₂ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ₃ is an alkyl group having 1 to 4 carbon atoms. And the group R ₄ represents an alkyl group having 1 to ₄ carbon atoms. A and A 'each represent an alkyl group having 4 to 12 carbon atoms;
It is a cycloalkyl group, an aryl group or an aralkyl group, both of which may be the same or different. n and m are molar ratios indicating the ratio of the number of each monomer to the total monomers in the polymer, and n + m = 1,
0 <n ≦ 1 and 0 ≦ m <1. The fact that the polysilane compound represented by the general formula (I) used in the present invention is objectively distinguished from known polysilane compounds will be described below.

That is, conventionally known polysilane compounds are generally obtained by using a dichlorosilane monomer as a starting material, performing halogen elimination from the monomer using a Na catalyst, and polymerizing the monomer, as described above. For this reason, most of them have a halogen residue at the terminal.

When a conventional polysilane compound having such a halogen residue is used as a constituent material of a photoreceptor layer of an electrophotographic photoreceptor, the obtained electrophotographic photoreceptor has the following problems. It is not worthy of practical use. That is, in the electrophotographic photoreceptor having a light receiving layer composed of the conventional polysilane compound,
When an image is formed by using this, the halogen residue serves as a trap for charge transfer, resulting in a residual potential. In addition, when performing repetitive charging and exposure, the residual potential increases, and accordingly the bright portion potential increases, resulting in poor durability. In addition to these issues, there are other issues as well. That is, when the halogen residue of the conventional polysilane compound having a halogen residue interposed therein constituting the photoreceptor is a Cl group, if there is water, the Cl group reacts with the water to react with hydrogen chloride gas (HCl ) Is generated, and as a result, a conductive portion of the substrate of the electrophotographic photoreceptor in contact with the light receiving layer is corroded, resulting in poor conduction, resulting in an image defect.

On the other hand, the polysilane compound used in the present invention is:
It is represented by the above general formula (I) and has a weight average molecular weight of 6,000 to 200,000 and has no halogen group, and is specified by a side reaction like the above-mentioned conventional polysilane compound. It is characterized by its distinctive features such as no dissolution, easy dissolution in organic solvent and complete dissolution without turbidity, and excellent film-forming ability to make the resulting film transparent without local defects. It is something that can be done.

The present inventors have made a polysilane compound having a weight average molecular weight of 6,000 to 200,000 and having no halogen residue, which is represented by the above general formula (I), a constituent material of a light receiving layer of an electrophotographic photoreceptor. It was examined through experiments whether or not it was suitable. As a result, the following was found.

That is, the following was found about the polysilane compound itself. (I) It is stable without any side reaction under the use environment: (ii) It is easily soluble in an organic solvent and can be completely dissolved without turbidity: and (iii) It has excellent film-forming ability: (iv) The resulting film is in a transparent state without local defects: and (v) has excellent charge transport ability and very fast charge mobility is observed.

When the polysilane compound was applied to a light receiving layer of an electrophotographic photoreceptor, the following was found. That is, (a) a photoreceptor for electrophotography which provides a high-sensitivity, defect-free and high-quality image: (b) no trap is generated, and the residual potential upon exposure is extremely small: (c) excellent charge A transport layer can be realized: and (d) when the polysilane compound is used in combination with a charge generating substance, it is possible to provide an electrophotographic photoreceptor having excellent electrophotographic properties.

As described above, the present invention relates to a light-receiving layer of an electrophotographic photoreceptor, which comprises a polysilane compound having a weight average molecular weight of 6,000 to 200,000 and having no halogen residue. The electrophotographic photoreceptor having a light-receiving layer formed by using the polysilane compound is suitable as a constituent material of the present invention, and has been found to have the various advantages described above, and has been completed. It is.

Polysilane compound used in the present invention and its production method The polysilane compound represented by the above general formula (I) and having a weight average molecular weight of 6,000 to 200,000 used in the present invention has a chloro group or a side reaction product group. It has no organic group and all Si groups are replaced by specific organic groups having no oxygen.There is no toxicity, aromatic solvents such as toluene, benzene, xylene, dichloromethane, dichloroethane, chloroform, tetrachloride It is easily soluble in halogenated solvents such as carbon and other solvents such as tetrahydrofuran (THF) and dioxane, and has excellent film forming ability. The film formed by using the polysilane compound has a uniform and uniform film thickness, has excellent heat resistance, is rich in hardness and is rich in toughness.

The polysilane compound represented by the above general formula (I) used in the present invention has a weight average molecular weight of 6,000 to 200,000 as described above, but has a solubility in a solvent and an ability to form a film. More preferred from the point of view, the weight average molecular weight is 8,000 to 120,000, and the most preferable one has a weight average molecular weight of 10,000 to 80,000.
belongs to.

Those having a weight average molecular weight of 6,000 or less do not exhibit the characteristics of a polymer and have no film forming ability. On the other hand, those having a molecular weight of 200,000 or more have poor solubility in a solvent, making it difficult to form a desired film.

The above-mentioned polysilane compound represented by the above general formula (I) used in the present invention may have terminal groups A and A 'when the film to be formed is particularly tough.
Is preferably a group selected from the group consisting of an alkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group, and an aralkyl group. In this case, the most preferred polysilane compound used in the present invention is a compound in which the terminal groups A and A 'are groups selected from an alkyl group having 5 to 12 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms. It is.

The above-mentioned polysilane compound used in the present invention can be synthesized as follows. That is, under a high-purity inert atmosphere free of oxygen and moisture, a dichlorosilane monomer is brought into contact with a condensation catalyst composed of an alkali metal to carry out halogen elimination and condensation polymerization to synthesize an intermediate polymer. The polymer is synthesized by separating the polymer from the reaction monomer, reacting the intermediate polymer with a predetermined halogen and organic reagent in the presence of a condensation catalyst composed of an alkali metal, and condensing an organic group to the polymer terminal. You.

In the above-mentioned synthesis operation, the dichlorosilane monomer, the intermediate polymer, the halogenated organic reagent, and the alkali metal condensation catalyst, which are the starting materials, all have high reactivity with oxygen and moisture, and therefore these oxygen and moisture are present. The desired polysilane compound described above cannot be obtained under an atmosphere in which the heat treatment is performed.

Therefore, the above-mentioned operation for obtaining the above-mentioned polysilane compound used in the present invention needs to be performed in an atmosphere in which neither oxygen nor moisture is present. For this reason, it is necessary to pay attention to all of the reaction vessels and the reagents used so that neither oxygen nor moisture is present in the reaction system. For example, for the reaction vessel,
Vacuum suction and argon gas replacement are performed in a blow box to prevent moisture and oxygen from adsorbing into the system. In any case, the argon gas to be used is dehydrated by passing through a silica gel column in advance and then deoxidizing by passing the copper powder through a column heated to 100 ° C.

The dichlorosilane monomer as a starting material is introduced into the reaction system after performing vacuum distillation using the above-described argan gas which has been deoxygenated immediately before introduction into the reaction system. The halogenated organic reagent for introducing a specific organic group and the solvent to be used are also introduced into the reaction system after being subjected to a deoxygenation treatment in the same manner as the dichlorosilane monomer. In the deoxidizing treatment of the solvent, the solvent is subjected to distillation under reduced pressure using the above-described deoxidized argon gas, and then further dehydrated with metallic sodium.

The above-mentioned condensation catalyst is used in the form of a wire or chip. The wire or chip is used in an oxygen-free paraffin-based solvent to prevent oxidation.

The dichlorosilane monomer as a starting material used in producing the polysilane compound represented by the above general formula (I) used in the present invention is a silane compound represented by a general formula: R ₁ R ₂ SiCl ₂ or This and a silane compound represented by the general formula: R ₃ R ₄ SiCl ₂ are selectively used.

As the above-mentioned condensation catalyst, an alkali metal which causes a condensation reaction by elimination of halogen is desirably used, and specific examples of the alkali metal include lithium, sodium and potassium, and among them, lithium and sodium are preferable.

The above-mentioned halogenated organic reagent is for introducing a substituent represented by A and A ', and comprises an alkali halide compound, a cycloalkyl halide compound, an aryl halide compound and an aralkyl halide compound. A suitable compound selected from the group, i.e. the general formula: A
-X and / or a general formula: A'-X (where X is Cl or Br), and an appropriate compound in specific examples described later is selectively used.

The general formula used in synthesizing the above-mentioned intermediate polymer: R ₁ R ₂ SiCl ₂ or a dichlorosilane monomer represented by the general formula: R ₃ R ₄ SiCl ₂ is dissolved in a predetermined solvent to form a reaction system. As the solvent, a paraffinic non-polar hydrocarbon solvent is desirably used. Preferred examples of the solvent include n-hexane, n-octane, and n-hexane.
-Nonane, n-dodecane, cyclohexane and cyclooctane.

Since the resulting intermediate polymer is insoluble in these solvents, it is convenient to separate the intermediate polymer from unreacted dichlorosilane monomer. The separated intermediate polymer is then reacted with the above-mentioned halogenated organic reagent. At this time, both are dissolved in the same solvent and used for the reaction. As the solvent in this case, an aromatic solvent such as benzene, toluene and xylene is preferably used.

In order to obtain a desired intermediate by condensing the above-mentioned dichlorosilane monomer using the above-mentioned alkali metal catalyst, the polymerization degree of the obtained intermediate polymer can be appropriately controlled by adjusting the reaction temperature and the reaction time. However, the reaction temperature at that time is desirably set between 60 ° C and 130 ° C.

One preferred embodiment of the method for producing the above-mentioned polysilane compound represented by the general formula (I) used in the present invention described above will be described below.

That is, the above-mentioned method for producing a polysilane compound used in the present invention comprises (i) a step of producing an intermediate polymer, and (ii) a step of introducing substituents A and A 'into the terminal of the intermediate polymer. .

The step (i) is performed as follows. That is, the inside of the reaction system of the reaction vessel was completely removed of oxygen and moisture, maintained at a predetermined internal pressure controlled by argon, charged with an oxygen-free paraffin-based solvent and an oxygen-free condensation catalyst. The chlorosilane monomer is charged, and the whole is heated to a predetermined temperature while stirring to condense the monomer. At this time, the degree of condensation of the dichlorosilane monomer is
The reaction temperature and reaction time are adjusted so that an intermediate polymer having a desired degree of polymerization is produced.

In this reaction, as shown in the following reaction formula (i), the chloro group of the dichlorosilane monomer and the catalyst cause a desalination reaction, and the Si groups repeatedly condense to form an intermediate polymer. I do.

In addition, a specific reaction operation procedure is to prepare a condensation catalyst (alkali metal) in a paraffin solvent,
The dichlorosilane monomer is added dropwise while stirring under heating. The degree of polymerization is confirmed by sampling the reaction solution.

A simple confirmation of polymerization can be made by volatilizing the sampling liquid to form a film. As the condensation proceeds and the polymer is formed, it becomes a white solid and precipitates from the reaction system. Here, the mixture is cooled, and the solvent containing the monomer is separated from the reaction system by decantation to obtain an intermediate polymer.

Next, the step (b) is performed. That is, the chloro group of the terminal group of the obtained intermediate polymer is subjected to desalting condensation using a halogenated organic agent and a condensation catalyst (alkali metal) to replace the polymer terminal group with a predetermined organic group. The reaction at this time is represented by the following reaction formula (ii).

Here, specifically, an aromatic solvent is added to and dissolved in the intermediate polymer obtained by condensation of the dichlorosilane monomer. Next, a condensation catalyst (alkali metal) is added, and a halogenated organic agent is added dropwise at room temperature. At this time, a halogenated organic agent is added in an amount of 0.01 to 0.1 times the amount of the starting monomer in order to compete with the condensation reaction between the polymer end groups. The mixture is gradually heated, and heated and stirred at 80 ° C to 100 ° C for 1 hour to perform a desired reaction.

After completion of the reaction, the mixture is cooled, and methanol is added to remove the alkali metal of the catalyst. Next, the produced polysilane compound is extracted with toluene and purified with a silica gel column.
Thus, the desired polysilane compound used in the present invention is obtained.

Specific examples of R ₁ R ₂ SiCl ₂ and R ₃ R ₄ SiCl ₂ Note): Note of the following compounds, a-2 to 16, 18, 20, 21, 23, 24
Is used for R ₁ R ₂ SiCl ₂ and a−1,2,11,17,19,22,23,25
Is used for R ₃ R ₄ SiCl ₂ .

_{(CH 3) 2 SiCl 2 a} -1 (CH ₃ ) ₂ CH) ₂ SiCl ₂ a-22 Specific examples of (CH ₃ ) ₃ C) ₂ SiCl ₂ a-25 AX and A′-X (CH ₃ ) ₂ CHCH ₂ Cl b-1 CH ₃ (CH ₂ ) ₄ Cl b-2 CH ₃ (CH ₂ ) ₅ Cl b-3 CH ₃ (CH ₂ ) ₁₀ Cl b-4 CH ₃ (CH ₂ ) ₅ Br b-14 CH ₃ (CH ₂ ) ₁₀ Br b-15 As the catalyst, an alkali metal is preferable.

As the alkali metal, lithium, sodium, and potassium are used. The shape is preferably a wire or a chip to increase the surface area.

Specific examples of the polysilane compound used in the present invention Note): X and Y in the above structural formulas each represent a polymerized unit of a monomer. And n is X / (X + Y), and m is Y /
Each is obtained by the calculation formula of (X + Y).

Electrophotographic Photoreceptor The electrophotographic photoreceptor of the present invention basically includes a conductive support and the above-mentioned polysilane compound provided on the support (that is, the above C-1 to C- And a light-receiving layer containing a polysilane compound selected from among 43). (The "light receiving layer" in the present invention
Means a layer provided on a conductive support as a whole. The light receiving layer may be composed of a single layer, or may be composed of a plurality of layers having separated functions.

A typical example of the electrophotographic photoreceptor of the present invention in which the light receiving layer is a single layer has a form schematically shown in FIG. In FIG. 1, 101 is a conductive support, and 102 is a light receiving layer containing the above-mentioned polysilane compound. In this case, the light receiving layer 102 contains the above-mentioned polysilane compound (that is, a substance that causes charge transport (charge transporting substance)) and a substance that causes charge generation (hereinafter, referred to as “charge generating substance”). This is a so-called photosensitive layer. An electrophotographic photoreceptor of the type shown in FIG. 1 is provided with an undercoat layer (barrier function and adhesive function) between a conductive support and the photosensitive layer (photoreceptive layer 102), if necessary. (Not shown), and a surface protective layer (not shown) for protecting the photosensitive layer (light receiving layer 102).

In the case of the electrophotographic photoreceptor of the embodiment shown in FIG. 1, the photosensitive layer (that is, the light receiving layer 102) contains a charge generating substance and a charge transporting substance (that is, the above-mentioned polysilane compound), and both substances are weight-weighted. The ratio (charge generating material: charge transporting material) is preferably 1:
Both substances are contained in a state of being present uniformly in the entire layer region at a ratio of 100 to 1: 1, more preferably 1:20 to 1: 3, and the layer thickness is preferably 4 to 30 μm, more preferably 7 or more
20 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, azo pigments, phthalocyanine pigments, anthrothro pigments, quinone pigments,
Examples include pyratron pigments, indigo pigments, quinacridone pigments, and pyrylium dyes. Examples of the inorganic charge generating substance include selenium, selenium-tellurium, and selenium-
Arsenic and the like.

The formation of the photosensitive layer (that is, the light receiving layer 102) of the electrophotographic photosensitive member of the type shown in FIG. 1 can be performed, for example, as follows. That is, first, a predetermined amount of the above-described charge generating substance is dispersed in an appropriate solvent to prepare a suspension,
A predetermined amount of a polysilane compound (C described above) is added to the obtained suspension.
-1 to C-43) to prepare a coating solution. The obtained coating liquid is coated on the surface of the conductive support in an amount such that the layer thickness after drying becomes within the above-mentioned predetermined thickness through an appropriate coating means, and the formed liquid coat is formed by a known means. Dry and solidify. 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 undercoat layer described above is provided on an electrophotographic photoreceptor of the type shown in FIG. 1, the layer thickness is preferably 4 to 30 μm.
m, more preferably 7 to 20 μm.

The undercoat layer is made of casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66,
Nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane and aluminum oxide. When forming the undercoat layer, if the material for the undercoat layer to be used is soluble in a solvent, it is dissolved in an appropriate solvent to prepare a coating solution,
Further, when the material is insoluble in a solvent, it is dispersed in a binder resin solution to prepare a coating liquid,
The obtained coating liquid is coated on the surface of the conductive support 101 in the same manner as in the formation of the photosensitive layer described above to form a liquid coat, which is dried and solidified.

When the above-mentioned surface protective layer is provided on an electrophotographic photoreceptor of the type shown in FIG.
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 control agent and a deterioration inhibitor.

The surface protective layer is formed by dissolving the resin in an appropriate solvent to prepare a coating solution, and forming the obtained coating solution in the same manner as in the formation of the photosensitive layer described above. This is performed by coating the surface of the photosensitive layer to form a liquid coat, followed by drying and solidification.

When the above-mentioned resistance controlling agent or deterioration preventing agent is contained in the surface protective layer, by dispersing such an additive uniformly in the coating liquid for the surface protective layer, the formed surface protective layer can use such an additive. Will be included.

When the electrophotographic photoreceptor of the present invention has a photoreceptive layer composed of a plurality of layers separated in function, it typically has the form shown in FIG. 2 or FIG. That is, the electrophotographic photoreceptor of the present invention in the form shown in FIG. 2 comprises, on a conductive support 201, a charge generation layer 202 containing a charge generation substance and a charge transport layer 2 containing the above-mentioned polysilane compound.
03 are laminated in this order from the support 201 side. The electrophotographic photoreceptor of the present invention in the form shown in FIG. 3 has a charge transport layer 302 containing the above-mentioned polysilane compound and a charge generation layer 303 containing a charge generating substance on a conductive support 301. Are laminated in this order from the support 301 side.

The electrophotographic photoreceptor of the present invention in the form shown in FIGS. 2 and 3 is the same as the electrophotographic photoreceptor in the form shown in FIG. (Not shown)
And / or a surface protection layer (not shown).

That is, the undercoat layer is provided between the conductive support 201 and the charge generation layer 202 in the case of the electrophotographic photoreceptor of the embodiment shown in FIG. In the case of a photoconductor, it is provided between the conductive support 301 and the charge transport layer 302.

The surface protective layer is provided on the charge transport layer 203 in the case of the electrophotographic photoreceptor of the embodiment shown in FIG.
In the case of the electrophotographic photoconductor of the embodiment shown in FIG. 3, it is provided on the charge generation layer 303.

In the electrophotographic photosensitive member having the charge generating layer (202 or 303) and the charge transporting layer (203 or 302) in the form shown in FIG. 2 and FIG. For those exhibiting characteristics, the thickness of both layers is one of the important requirements. That is, in the case of the electrophotographic photoreceptor of the embodiment shown in FIG.
The thickness of the charge transport layer 203 is preferably 1 to 5 μm, more preferably 0.05 to 2 μm, and the charge transport layer 203 is preferably 4 to 30 μm, more preferably 7 to 20 μm.

In the case of the electrophotographic photoreceptor of the form shown in FIG. 3, the charge transport layer 302 has a thickness of preferably 4 to 30 μm, more preferably 7 to 20 μm, and the charge generation layer 303 has a thickness of preferably 1 to 15 μm. More preferably, the thickness is 3 to 10 μm.

When a lower layer is provided on the electrophotographic photoreceptor shown in FIG. 2 or 3, the thickness of the lower layer is preferably 4 to 30 μm.
m, more preferably 7 to 20 μm. Similarly, when a surface protective layer is provided, its thickness is preferably 0.1 to 5
μm.

As the charge generating substance contained in the charge generating layer 202 or 303, a known organic charge generating substance or a known inorganic charge generating substance 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-tellurium, selenium-arsenic, and the like.

The charge generation layer 202 or 303 can be formed by a method of depositing the charge generation substance by a known means or a method of preparing a coating liquid containing the charge generation substance, applying the coating liquid, and drying and solidifying the coating liquid. Of these two methods, the latter method is more preferable. That is, according to the latter method,
The distribution of the charge generating substance in the desired state on the charge generating layer to be formed can be easily achieved. The specific content of the latter method is
Using a suitable dispersion medium, the charge generating substance is introduced into a suitable solvent together with the dispersion medium to prepare a coating liquid in which the charge generating substance is uniformly dispersed, and then applied to form a liquid coat. The liquid coating is dried and solidified to form the charge generation layer 202 or 303.

Desirable examples of the dispersion medium include a so-called binder resin such as an insulating resin and an organic photoconductive polymer. Specific examples of such a binder resin include polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy resin, cellulose resin, acrylic resin, polyurethane, and the like. 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 used depends on the content (weight ratio) in the finally formed charge generation layer (202 or 203).
, Preferably 80% by weight or less, more preferably 40% by weight
It is desirable to do the following.

In addition, as the solvent, a solvent that dissolves the above-described binder resin and allows the above-described charge generating substance to be uniformly dispersed in the dissolved binder resin is selectively used. Specific examples of such solvents 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: methyl acetate, ethyl acetate Esters such as toluene: aromatics such as toluene, xylene and chlorobenzene: alcohols such as methanol, ethanol and 2-propanol: chloroform, methylene chloride, dichloroethylene,
Examples include aliphatic halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene.

For 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 can be formed by the same method as in the formation of the charge generation layer (202 or 303). That is, the charge transport layer is
A coating liquid is prepared by dissolving a polysilane compound selected from the above C-1 to C-43 in an amount of preferably 5 to 30% by weight, more preferably 10 to 20% by weight, based on the solvent. This is applied to form a liquid coat, and the liquid coat can be formed by drying and solidifying. Examples of the solvent include aromatic solvents such as benzene, toluene, and xylene; halogen solvents such as dichloromethane, dichloroethane, and chloroform; in addition to these solvents, 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).

In the case of providing the undercoat layer and / or the surface protective layer in the electrophotographic photosensitive member of the embodiment shown in FIG. 2 or the electrophotographic photosensitive member of the embodiment shown in FIG. It can be formed by the same method as described for the electrophotographic photosensitive member shown in FIG.

The conductive support (101, 201, 301) of the electrophotographic photoreceptor of the present invention in the form shown in FIGS. 1, 2 and 3 will be described. First, the shape may be any shape such as a cylindrical shape, a belt shape, and a plate shape. Next, as for the constituent material, the whole may be a conductive member,
Alternatively, the base may be an insulating member, and the surface on which the light receiving layer is provided may be a member 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 alloys and stainless steel. For the latter case, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, a member in which the above-described metal coating is formed on the surface of a plastic base member such as an acrylic resin by a known vacuum deposition method, on the surface of the plastic base member, A member in which conductive particles such as titanium oxide, tin oxide, carbon black, and silver are coated using a suitable binder resin, a member in which the conductive particles are impregnated into an impregnating base member such as paper, plastic, and the like. Can be mentioned. 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 photoreceptors shown in FIGS. 1 to 3 described above, when the next constituent layer is formed on the previously formed constituent layer, the solvent to be used is first formed. It is important to select and use a solvent that does not dissolve the constituent layer.

The electrophotographic photoreceptor of the present invention described above 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 the like.

(Production example of polysilane compound used in the present invention)

Hereinafter, a specific production method of the polysilane compound used in the present invention will be described with reference to production examples,
In addition, the usefulness of the polysilane compound will be described.

In the production examples and comparative production examples described below, the presence or absence of Cl groups in the product was first checked, and the presence of Cl groups was quantified, and the amount of the product was determined. Expressed in millimolar equivalents per 1000 grams.

In addition, the obtained product was confirmed by a FT-IR and / or UV spectrum whether or not it was a polysilane compound having a main chain composed of Si-Si bonds having a long-chain structure. Further, in conjunction with this, the presence or absence of the bond of the side chain substituent was determined by FT-IR.
And / or by confirming the protons in the substituents by FT-NMR.

From the results obtained above, the structure of the synthetic product was determined.

The above-mentioned confirmation of the presence or absence of Cl groups in the product was performed using a fluorescent X-ray analyzer (fully automatic fluorescent X-ray analyzer system 3080: manufactured by Rigaku Corporation). At that time, trimethylchlorosilane (manufactured by Nitrogen Co., Ltd.) was prepared as a standard sample, and diluted 1,5,10,50,100 times to prepare standard solutions.
The amount of Cl group was measured using a line analyzer, and a calibration curve was obtained based on the obtained results. On the other hand, for the product as a test sample, 1 g of the product is dissolved in dehydrated toluene to prepare a test sample having a total volume of 10 ml. The amount of Cl group was based on the line.

The measurement by FT-IR was performed by preparing a KBr pellet of a test sample, setting this in a Nicoet FT-IR750 (manufactured by Nicole Japan), and measuring. Also, FT
Measurements by -NMR can be prepared by dissolving the test sample in CDCl _3, this
The measurement was performed by setting to FT-NMR FX-9Q (manufactured by JEOL Ltd.).

In the UV spectrum, when the polysilane compound is of a low molecular weight, the spectrum is shifted to the short wavelength side, and when the polysilane compound is of a high molecular weight, the spectrum is shifted to the long wavelength side. Chemistry (Pure & Applied Chemistry) 54 , No.5.p
p. 1041-1050 (1982).

Production Example 1 A three-necked flask was prepared in a blow box in which vacuum suction and argon substitution were performed, and a reflux condenser, a thermometer, and a dropping funnel were attached to the flask, and argon gas was passed through a bypass pipe of the dropping funnel.

100 g of dehydrated dodecane and 0.3 mol of metal wire were charged into the three-necked flask, and heated to 100 ° C. with stirring. Next, 0.1 mol of dichlorosilane monomer (manufactured by Chisso Corporation) (a-7) was dissolved in 30 g of dehydrated dodecane, and the prepared solution was slowly dropped into the reaction system.

After the addition, the mixture was condensed at 100 ° C. for 1 hour to precipitate a white solid. Thereafter, the mixture was cooled, decanted of dodecane, and further added with 100 g of dehydrated toluene to dissolve the white solid.
Mole was added. Next, a solution prepared by dissolving 0.01 mol of n-hexyl chloride (manufactured by Tokyo Kasei) (b-3) in 10 ml of toluene was slowly added dropwise to the reaction system while stirring, and the mixture was heated at 100 ° C. for 1 hour. . Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to treat excess metal sodium. This produced a suspension and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and then developed and purified by silica gel column and chromatography.
The product was obtained with a yield of. For this product, the Cl
As determined by the method for measuring the group content, no Cl group was found (ie, 0.00 mmol equivalent in 10,000 grams of sample).

The weight average molecular weight of this product was determined by the GPC method in THF.
It was 75,000 when developed and measured (with polystyrene as standard). Then, the product was subjected to FT-IR measurement and then FT-NMR measurement by the above-mentioned method, and it was found that there was no Si-Cl engagement, Si-O-Si bond, or Si-OR bond at all. As a result, the product was found to be a polysilane compound having the above-mentioned C-1 structure.

 The above results are shown in Table 4.

Production Example 2 A three-necked flask was prepared in a blow box in which vacuum adsorption and argon substitution were performed, and a reflux condenser, a thermometer, and a dropping funnel were attached to the flask, and argon gas was passed through a bypass pipe of the dropping funnel. .

1000 grams of dehydrated dodecane and 1 meter in this three-necked flask
Charge 0.3 mole of m-square metallic lithium and stir for 100
Heated to ° C. Next, a solution prepared by dissolving 0.1 mol of dichlorosilane monomer (manufactured by Chisso Corporation) (a-7) in 30 g of dehydrated dodecane was slowly dropped into the reaction system. After dropping, by condensation polymerization at 100 ° C for 2 hours,
A white solid precipitated. After cooling, decant the dodecane, and further add 100 grams of dehydrated toluene to dissolve the white solid and add metallic lithium 0.
02 mol was added.

Next, chlorobenzene (manufactured by Tokyo Kasei) (b-5) 0.02
A solution prepared by dissolving a mole in 10 ml of toluene was slowly added dropwise to the reaction system with stirring, and the mixture was heated at 100 ° C. for 1 hour. Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to treat excess metallic lithium. This produced a suspension layer and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and developed and purified by silica gel column and chromatography to obtain polysilane compound No. 2 (structural formula: C-3). Yield 72
% And the weight average molecular weight was 92,000. The results are shown in Table 4.

Production Example 3 A three-necked flask was prepared in a blow box in which vacuum suction and argon substitution were performed, and a reflux condenser, a thermometer, and a dropping funnel were attached to the flask, and argon gas was passed through a bypass pipe of the dropping funnel.

100 g of dehydrated n-hexane and 0.3 mol of 1 mm square metal sodium were charged into the three-necked flask and heated to 80 ° C. with stirring. Next, a solution prepared by dissolving 0.1 mol of dichlorosilane monomer (manufactured by Chisso Corporation) (a-7) in dehydrated n-hexane was slowly dropped into the reaction system. After the dropping, condensation polymerization was carried out at 80 ° C. for 3 hours to precipitate a white solid. Thereafter, the mixture was cooled, n-hexane was decanted, and 1000 g of dehydrated toluene was added to dissolve the white solid.
01 mole was added. Next, a solution prepared by dissolving 0.01 mol of benzyl chloride (manufactured by Tokyo Chemical Industry) (b-12) in 10 ml of toluene was slowly added dropwise to the reaction system while stirring, and the mixture was heated at 80 ° C. for 1 hour. Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to treat excess metal sodium. This produced a suspension and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and developed and purified by silica gel column and chromatography to obtain polysilane compound No. 3 (structural formula: C-4). Yield 61
% And the weight average molecular weight was 47,000. The results are shown in Table 4.

In this polysilane compound, unreacted Si-
IR attributed to Cl, by-product Si-O-Si, Si-OR
There was no absorption.

Production Examples 4 and 5 Synthesis was carried out in the same manner as in Example 3 using the dichlorosilane monomer and the terminal group treating agent shown in Table 1 to obtain polysilane compound No. 4 (structural formula: C-6) and polysilane compound No. Five
(Structural formula: C-2) was obtained in yields of 60% and 62%, respectively. In this polysilane compound, unreacted Si
-Cl, I- attributed to by-products Si-O-Si, Si-OR
There was no R absorption. The identification results are summarized in Table 4.

Comparative Production Example 1 Synthesis was carried out in the same manner as in Example 3, except that the dichlorosilane monomer (manufactured by Chisso Corporation) (a-7) was condensed and the terminal group of the polymer was not treated. Polysilane compound No. D-1 having a structural formula shown in Table 4 was obtained.
The yield was 60% and the weight average molecular weight was 46,000.
The results are shown in Table 4.

In this polysilane compound, IR absorption attributed to unreacted Si-Cl and by-product Si-OR was observed at the terminal group.

Production Examples 6 to 10 Polymerization was carried out in the same manner as in Example 3 except that the reaction time was changed as shown in Table 2 using the dichlorosilane monomers shown in Table 2. The compounds shown in Table 2 were used as the terminal group treating agent. The synthetic product was purified in the same manner as in Production Example 3. Thus, the polysilane compounds No. 6 to
I got 10.

The yield and weight average molecular weight of each of the obtained polysilane compounds were as shown in Table 4.

In addition, unreacted in any polysilane compound
There was no IR absorption attributed to Si-Cl and the by-products Si-O-Si and Si-OR.

Comparative Production Example 2 Synthesis was carried out in exactly the same manner as in Production Example 6, except that the reaction time of the dichlorosilane monomer was changed to 10 minutes, to obtain a polysilane compound No. D-2 shown in Table 4.

The yield and weight average molecular weight of the obtained polysilane compound were as shown in Table 4.

In addition, unreacted Si was added to the obtained polysilane compound.
-Cl, I- attributed to by-products Si-O-Si, Si-OR
There was no R absorption.

Production Examples 11 to 14 Synthesis was performed in the same manner as in Example 1 using the dichlorosilane monomer and the terminal group treating agent shown in Table 3 to obtain polysilane compounds No. 11 to No. 14 shown in Table 4. Was. The yield and weight average molecular weight of each of the obtained polysilane compounds were as shown in Table 4.

Comparative Production Example 3 A three-necked flask was prepared in a blow box in which vacuum suction and argon substitution had been performed, and a reflux condenser, a thermometer, and a dropping funnel were attached to the flask, and argon gas was passed through a bypass pipe of the dropping funnel.

100 g of dehydrated dodecane and 0.3 mol of metal wire were charged into the three-necked flask, and heated to 100 ° C. with stirring. Next, a solution prepared by dissolving 0.1 mol of dichlorosilane monomer (manufactured by Chisso Corporation) in 30 g of dehydrated dodecane was slowly dropped into the reaction system. After the dropwise addition, a white solid was precipitated by condensation polymerization at 100 ° C. for 1 hour. Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to treat excess metal sodium.

Next, the white solid was collected by filtration and washed repeatedly with n-hexane and methanol to obtain a polysilane compound No. D shown in Table 4.
-3 was obtained.

This polysilane compound is toluene, chloroform, TH
It was insoluble in organic solvents such as F. The results were as shown in Table 4.

Comparative Production Example 4 A three-necked flask was prepared in a blow box in which vacuum suction and argon substitution were performed, and a reflux condenser, a thermometer, and a dropping funnel were attached to the flask, and argon gas was passed through a bypass pipe of the dropping funnel.

100 g of dehydrated dodecane and 0.3 mol of metal wire were charged into the three-necked flask, and heated to 100 ° C. with stirring.

Next, a solution prepared by dissolving 0.1 mol of diphenyldichlorosilane monomer (manufactured by Chisso Corporation) in 30 g of dehydrated dodecane was slowly dropped into the reaction system. After the dropwise addition, a white solid was precipitated by condensation polymerization at 100 ° C. for 1 hour.

Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to treat excess metal sodium.

Next, the white solid was collected by filtration and washed repeatedly with n-hexane and methanol to obtain a polysilane compound No. D shown in Table 4.
-4 was obtained.

This polysilane compound is toluene, chloroform, TH
It was insoluble in organic solvents such as F. The results are shown in Table 4.

Examples Hereinafter, an electrophotographic photoreceptor having a light-receiving layer containing the polysilane compound of the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Absent.

Example 1 An electrophotographic photoreceptor 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, the charge generation layer 202 was formed on the aluminum substrate surface as follows. That is, 10 parts by weight of chloroaluminum phthalocyanine and 5 parts by weight of polyvinyl butyral were dispersed in a ball mill in 90 parts by weight of methyl ethyl ketone to form a charge generation layer 20.
Prepare a coating solution for 2 and apply the obtained coating solution to the aluminum substrate surface with a wire bar having a thickness of 0.3 μm after drying to form a liquid coat, and then dry to form a 0.3 μm
A thick charge generation layer 202 was formed. Then, a coating liquid for the charge transport layer 203 was prepared by dissolving 20% by weight of the polysilane compound (polysilane compound No. 1 shown in Table 4) obtained in Production Example 1 in 80% by weight of toluene. . On the surface of the charge generation layer 202, on which the obtained coating liquid was previously formed, the film thickness after drying was 10
A liquid coat was formed by coating with a wire bar having a thickness of μm, and dried to form a charge transport layer 203 having a thickness of 10 μm, thereby obtaining an electrophotographic photoconductor (sample No. 1). The obtained electrophotographic photosensitive member samples were evaluated from various viewpoints.

That is, the photoreceptor sample for electrophotography 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 held for 1 second in a dark place. The light sensitivity was examined by exposing at 2.5 lux, and the charge was removed by strong exposure (illuminance: 20 lux · sec).

Regarding the charging characteristics, the potential (V ₁ ) one second after corona charging
The amount of exposure (E1 / 2) required to attenuate the was measured.

Further, to measure the residual potential V _SL after strong exposure, the initial residual potential was V ⁰ _SL.

Further, the electrophotographic photoreceptor sample was prepared using Canon KK PPC.
A photoconductor drum cylinder of the copying machine NP-150Z was pasted, set on the copying machine and copied, and the initial image was evaluated. Then 500 copies are made continuously,
The image after copying was evaluated.

Next, the electrophotographic photoreceptor sample on the photoreceptor drum cylinder after the 500 copies was taken out of the copying machine, removed from the photoreceptor drum cylinder, and the electrophotographic paper tester Model Set the SP-428 to check the charging characteristics, and change the residual potential (V _SL ) (ΔV _SL )
Was measured.

 The obtained evaluation results were as shown in Table 5.

Examples 2 to 5 The polysilane compounds (polysilane compounds No. 2, 3, 4 and 5 shown in Table 4) obtained in Production Examples 2, 3, 4 and 5 were used as materials for forming the charge transport layer. Except for Example 1
In the same manner as described above, four types of electrophotographic photosensitive members of the type shown in FIG. 2 were prepared (samples No. 2 to No. 5).

Each of the obtained photoreceptor samples was evaluated in the same manner as in Example 1. The obtained evaluation results were as shown in Table 5.

Comparative Example 1 In the same manner as in Example 1 except that the polysilane compound obtained in Comparative Production Example 1 (polysilane compound No. D-1 shown in Table 4) was used as a material for forming a charge transporting layer, FIG. Electrophotographic photoreceptors of the type shown were prepared (Sample No. E-
1).

The obtained photoreceptor samples were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 5.

Examples 6 to 10 Forming a charge transport layer using each of the polysilane compounds obtained in Production Examples 6, 7, 8, 9 and 10 (polysilane compounds No. 6, 7, 8, 9 and 10 shown in Table 4) Four types of electrophotographic photosensitive members of the type shown in FIG. 2 were prepared in the same manner as in Example 1 except that the materials were used (samples No. 6 to No. 10).

Each of the obtained photoreceptor samples was evaluated in the same manner as in Example 1. The obtained evaluation results were as shown in Table 5.

Comparative Example 2 An electrophotographic photosensitive member of the type shown in FIG. 2 (sample No. E-
2) was attempted. The steps up to the formation of the charge generation layer 202 were performed in the same manner as in Example 1. Then, the polysilane compound obtained in Comparative Production Example 2 (polysilane compound shown in Table 4)
No. D-2 was dissolved in toluene to prepare a coating solution for forming the charge transport layer 203, and the coating solution was used to form the charge generation layer 202 formed earlier.
After drying, a liquid coating was formed by applying an amount such that the film thickness became 10 μm, and then subjected to drying. As a result, cracks occurred, and a photoreceptor could not be obtained.

Examples 11 to 14 Four types of electrophotographic photosensitive members of the type shown in FIG. 2 were produced (samples Nos. 11 to 14).

As the support 201, an aluminum substrate having a size of 10 cm × 1.0 cm and a thickness of 50 μm was used. Regarding the formation of the charge generation layer 202, the diazo pigment 10 represented by the following structural formula (I)
Parts by weight and 5 parts by weight of polybutylbutyral were dispersed in a ball mill in 90 parts by weight of methyl ethyl ketone to prepare a coating solution.
An amount of 0.2 μm was applied by a wire bar to form a liquid coat, and then dried to form a 0.2 μm thick charge generation layer 202. For the charge transport layer 203, the polysilane compound used was changed for each sample. That is, each of the polysilane compounds obtained in Production Examples 11 to 14 (No. 1 shown in Table 4)
1 to 14 polysilane compounds). The formation of the charge transport layer 203 of each sample using these polysilane compounds was performed in the same manner as in Example 1. Each of the obtained photoreceptor samples was evaluated by the same evaluation method as in Example 1.
The obtained evaluation results were as shown in Table 5.

Comparative Examples 3 to 4 The respective polysilane compounds (polysilane compounds of No. D-3 and No. D-4 shown in Table 4) obtained in Comparative Production Examples 3 and 4 were used as materials for forming the charge transport layer. The two electrophotographic photosensitive members No.E were used in the same manner as in Example 1 except that
-3 and No. E-4). However, No.D-3
No. D-4 and No. D-4 were insoluble in the prescribed organic solvents, and the desired photoreceptors could not be obtained.

Examples 15 to 19 Five types of electrophotographic photoreceptors of the type shown in FIG. 2 were produced (samples Nos. 15 to 19).

As the support 201, an aluminum substrate having a size of 10 cm × 10 cm and a thickness of 50 μm was used. Regarding the formation of the charge generation layer 202, the diazo pigment 10 represented by the following structural formula (II)
5 parts by weight of polycarbonate and 5 parts by weight of polycarbonate were dispersed in a ball mill in 90 parts by weight of tetrahydrofuran to prepare a coating liquid.
After drying the coating liquid on the surface of the aluminum substrate, a film thickness of 0.3 was obtained.
A liquid coat was formed by coating with an amount of μm using a wire bar, and dried to form a charge generation layer 202 having a thickness of 0.3 μm. For the charge transport layer 203, the polysilane compound used was changed for each sample. That is, the respective polysilane compounds (Nos. 1 to 5 shown in Table 4) obtained in Production Examples 1 to 5 were used. The formation of the charge transport layer 203 of each sample using these polysilane compounds was performed in the same manner as in Example 1. Each of the obtained photoreceptor samples was evaluated by the same evaluation method as in Example 1. The obtained evaluation results were as shown in Table 5.

Example 20 An electrophotographic photoreceptor of the type shown in FIG. 3 (sample No. 2
0) was prepared.

As the support 301, an aluminum substrate having a size of 10 cm × 10 cm and a thickness of 5 μm was used. First, a charge transport layer 302 was formed on the surface of the aluminum substrate. That is, Production Example 1
20 parts by weight of the polysilane compound obtained in the above (polysilane compound No. 1 shown in Table 4) was dissolved in 80 parts by weight of toluene to prepare a coating liquid for forming the charge transport layer 302, and the obtained coating liquid was obtained. Is applied to the aluminum substrate surface with a wire bar having a thickness of 10 μm after drying to form a liquid coat,
After drying, a charge transport layer 302 having a thickness of 10 μm was formed. Then, 5 parts by weight of dibromoanthanthrone (manufactured by Hoechst) represented by the following structural formula (III) and 10 parts by weight of the above-mentioned polysilane compound No. 1 were dispersed in a 85 wt. A coating liquid for forming 303 is prepared, and the obtained coating liquid is applied to the surface of the previously formed charge transporting layer 302 with a wire bar having a thickness of 3 μm after drying to form a liquid coat, followed by drying. As a result, a charge generation layer 303 having a thickness of 3 μm was formed to obtain a photoconductor for electrophotography (sample No. 20). The obtained electrophotographic photosensitive member sample was evaluated by the evaluation method in Example 1. The obtained evaluation results were as shown in Table 5.

Comparative Example 5 The charge transport layer 302 was formed using the polysilane compound obtained in Comparative Production Example 1 (polysilane compound No. D shown in Table 4).
An electrophotographic photoreceptor of the type shown in FIG. 3 (sample No. E-5) was produced in the same manner as in Example 20, except that -1) was adopted. The obtained electrophotographic photosensitive member sample was evaluated by the same evaluation method as in Example 1. The obtained evaluation result is the fifth
As shown in the table.

Comparative Example 6 In Example 20, polysilane compound No. 1 was used in forming charge generation layer 303, and polysilane compound No. D-1 was used.
A photoreceptor for electrophotography (Sample No. E-6) was prepared in the same manner as in Example 20, except that the composition was changed to. The obtained electrophotographic photosensitive member sample was evaluated by the same evaluation method as in Example 1. The evaluation samples obtained were as shown in Table 5.

Example 21 An electrophotographic photosensitive member of the type shown in FIG. 1 (sample No. 2
1) was prepared. As the support 101, an aluminum substrate having a size of 10 cm × 10 cm and a thickness of 5 μm was used. Photosensitive layer 102
Was formed as follows. That is, the following structural formula (I
V) Perylene (product name: Novo Palm Blade BL)
5 parts by weight of the polysilane compound obtained from Hoechst (polysilane compound No. 14 shown in Table 4) 20
A part by weight was dispersed in a ball mill in 75 parts by weight of toluene to prepare a coating liquid. The obtained coating solution is applied to the surface of the aluminum substrate by a wire bar so as to have a film thickness of 12 μm after drying to form a liquid coat.
Formed two. Thus, photoreceptor for electrophotography (Sample No. 21)
I got The obtained electrophotographic photosensitive member sample was evaluated by the same evaluation method as in Example 1. The obtained evaluation results were as shown in Table 5.

Comparative Example 7 An electrophotographic photoconductor (sample No. E-7) was prepared in the same manner as in Example 21, except that the polysilane compound No. 14 was replaced with the above-mentioned polysilane compound No. D-1. Obtained. The obtained electrophotographic photosensitive member sample was evaluated by the same evaluation method as in Example 1. The obtained evaluation results were as shown in Table 5.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an electrophotographic photoreceptor provided with a single light-receiving layer according to the present invention. 2 and 3 are schematic cross-sectional views of an electrophotographic photoreceptor in which the light receiving layer provided by the present invention is composed of a plurality of layers. In the figure, 101, 201, 301 ... conductive support, 102 ... photosensitive layer, 202, 303 ... charge generation layer, 203, 302 ... charge transport layer.

Claims (2)

(57) [Claims] 1. An electrophotographic photoreceptor having a light-receiving layer on a conductive support, wherein the light-receiving layer comprises a polysilane compound represented by the general formula (I) and having a weight average molecular weight of 6,000 to 200,000. An electrophotographic photoreceptor characterized by containing: Wherein R ₁ is an alkyl group having 1 or 2 carbon atoms, R ₂ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ₃ is an alkyl group having 1 to 4 carbon atoms. And the group R ₄ represents an alkyl group having 1 to ₄ carbon atoms. A and A 'each represent an alkyl group having 4 to 12 carbon atoms;
It is a cycloalkyl group, an aryl group or an aralkyl group, both of which may be the same or different. n and m are molar ratios indicating the ratio of the number of each monomer to the total monomers in the polymer, and n + m = 1,
0 <n ≦ 1 and 0 <m <1. ) 2. An electron containing a polysilane compound according to claim 1, wherein in the general formula (I), A and A 'are each an alkyl group having 5 to 12 carbon atoms or a cycloalkyl group. Photoreceptor.