JP2002023400A - Organic electronic device, electrophotographic photoreceptor, electrophotographic device for image formation and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronic device and an electrophotographic photoreceptor having high photoelectric characteristics and durability which are accurately and easily manufactured and to provide an electrophotographic device for image formation and a process cartridge equipped with the above electrophotographic photoreceptor in which sufficiently good quality of images can be obtained for a long time. SOLUTION: The organic electronic device has a supporting body and a layer containing an organic silicon compound laminated on the supporting body. The silicon compound is expressed by general formula (1): W-[D-SiR3-aQa]b, wherein W is a photofunctional organic group, D is a bivalent functional group, R is a hydrogen atom or the like, Q is a hydrolysable group, and a and b are integers. The peak area (S1) of the layer containing the organic silicon compound in the 29Si-NMR spectrum at-35 to 0 ppm and the peak area (S2) at -100 to -40 ppm satisfy the relation (2): 0.5<=S1/(S1+S2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an organic electronic device,
The present invention relates to an electrophotographic photosensitive member, an electrophotographic image forming apparatus, and a process cartridge, and more particularly, to an organic electronic device using a silicon-containing compound, an electrophotographic photosensitive member to which the organic electronic device is applied, and the electrophotographic photosensitive member And a process cartridge having the same.

[0002]

2. Description of the Related Art In recent years, in view of productivity, ease of material design, safety, etc., an electrophotographic photosensitive member using an organic photoconductive material, an organic electroluminescent device (organic EL device), an organic memory device, 2. Description of the Related Art Organic electronic devices such as organic wavelength conversion elements have attracted attention.

For example, electrophotographic image forming apparatuses such as plain paper copiers (PPCs), laser printers, LED printers, and liquid crystal printers have conventionally been made of materials such as selenium, arsenic-selenium, cadmium sulfide, zinc oxide, and a-Si. Inorganic photoreceptors (IPCs) used for organic photoconductors (IPCs) have been used, but in recent years, research and development of inexpensive organic photoreceptors (OPCs) that are excellent in manufacturability and disposability have been activated. Among organic photoconductors, a so-called function-separated type photoconductor in which a charge generation layer and a charge transport layer are stacked is excellent in electrophotographic characteristics such as sensitivity, chargeability, and its repetition stability. It is progressing rapidly.

Meanwhile, in the field of electrophotographic image forming apparatuses, copiers and printers using a contact charging system are increasing for reasons such as generation of oxidizing gas and suppression of power supply cost. In such an apparatus, a voltage having an AC component is applied to the photoconductor in order to stabilize the charging potential of the photoconductor, but when an organic photoconductor is used, the voltage between the photoconductor and the contact charging member is changed. The discharge breaks the bond of the binder resin contained in the photoreceptor surface layer and lowers the molecular weight. As a result, there is a problem that abrasion is significantly increased by mechanical cleaning such as a cleaning blade.

Further, materials used for organic electroluminescence devices are required to have a property that the morphological change of the film is not caused by the generated Joule heat. However, the required level is increasingly increasing from the viewpoint of a longer life and higher quality. It is expensive.

Therefore, various studies have been made to achieve chemical stability and durability against stresses such as heat and mechanical external forces which could not be obtained when a conventional photofunctional organic material was used. In particular, studies in the field of electrophotographic photoreceptors have been actively conducted.

[0007] For example, as one method of preventing abrasion of an electrophotographic photosensitive member, polymerization of a charge transporting material constituting a photosensitive member surface layer has been proposed. As such a polymer, US Pat. No. 4,806,443 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and bischloroformate; US Pat.
No. 806444 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and phosgene; US Pat. No. 4,801,517 discloses a polycarbonate obtained by polymerization of a bishydroxyalkylarylamine and bischloroformate or phosgene; US Pat. No. 4,937,165 and U.S. Pat. No. 4,959,288 describe polycarbonates obtained by the polymerization of certain dihydroxyarylamines or bishydroxyalkylarylamines with bischloroformates, and dihydroxyarylamines or bishydroxyalkylarylamines with bisphenols. Polyester obtained by polymerization with acyl halide; US Pat. No. 5,034,296 discloses arylamine having a specific fluorene skeleton Polycarbonates or polyesters; polyesters whose main chain specific bis styryl bis arylamine in JP-B-59-28903; U.S. Patent to No. 4,983,482 specification polyurethane
Are respectively disclosed. Also, Japanese Patent Application Laid-Open No. 61-209
No. 53, JP-A-1-134456, JP-A-1
JP-A-134457, JP-A-1-134462, JP-A-4-1330065, JP-A-4-133
No. 066 discloses a polymer in which a charge-transporting substituent such as hydrazone or triarylamine is pendant, and an electrophotographic photoreceptor using the same is proposed. However, in the electrophotographic photoreceptor using the above-mentioned polymer as a charge transporting material, in addition to the insufficient durability, a phenomenon that the electrophotographic properties such as sensitivity and residual potential are deteriorated easily occurs. There's a problem.

Another method for preventing abrasion of the electrophotographic photoreceptor is to disperse a low-molecular charge transport material in a binder resin or a precursor thereof and then cure the binder resin or a precursor thereof. Proposed. For example, JP-A-56-48637 and JP-B-56-428.
No. 63 discloses a technique using an acrylic polymer, and Japanese Patent Publication No. 5-47104, Japanese Patent Publication No. 60-22347, and Japanese Patent Publication No. 7-120051 disclose a technique using a silicon-based polymer or a precursor thereof. It has been disclosed. However, when the above method is used, the progress of the curing reaction of the binder resin does not proceed if a low molecular charge transporting material having a concentration (usually 30 to 50%) necessary for the electrophotographic photoreceptor to have sufficient characteristics is blended. Will be enough. As a result, with the use of the electrophotographic photoreceptor, the low-molecular-weight charge transport material escapes from between the binder resins, causing abrasion.

Further, as another method for preventing the abrasion of the photoreceptor, a method of providing a surface protective layer having high mechanical strength on the surface of the electrophotographic photoreceptor has been proposed, and a cross-linking curable resin has been studied as the material. Have been. Here, if the surface protective layer is composed of only a cross-linkable curable resin, the outermost surface layer of the photoreceptor becomes an insulating layer, and the light potential at the time of exposure increases, so that the development potential margin becomes narrower. It is necessary to sacrifice the photoelectric characteristics as a photoreceptor, for example, when the residual potential is increased, the image density is reduced particularly when printing is repeatedly performed for a long time.

As a method for imparting photoelectric properties to the surface protective layer of an electrophotographic photoreceptor, a method has been proposed in which a conductive metal oxide fine powder is dispersed in the surface protective layer as a resistance control material (Japanese Patent Application Laid-Open (JP-A) No. 2002-110630). No. 57-128344). However, since the resistance value of the conductive metal oxide fine powder generally has a high humidity dependency, when the electrophotographic photosensitive member obtained by such a method is used under high temperature and high humidity conditions, the surface of the photosensitive member is The resistance is reduced, and as a result, the electrostatic latent image is blurred and the image quality is significantly reduced.

Another method for imparting photoelectric properties to the surface protective layer of an electrophotographic photosensitive member is to disperse a low-molecular charge transport material in the binder resin and then cure the binder resin to cure the surface protective layer. Has been proposed (Japanese Patent Laid-Open No. 4-15659, etc.). According to this method, since the resistance of the photoreceptor surface does not show humidity dependency, it is possible to avoid a phenomenon in which image quality deteriorates under high temperature and high humidity conditions. Since the reaction is inhibited and the mechanical strength of the surface protective layer is reduced, even when a cross-linkable curable resin having sufficiently high mechanical strength alone is used, an electrophotographic photosensitive material having sufficiently high mechanical strength is used. It was difficult to get a body.

Further, as a method for imparting photoelectric properties and mechanical strength to the surface protective layer of an electrophotographic photosensitive member, a charge transporting material having a reactive functional group is reacted with a thermoplastic binder resin to form a surface. Proposals have been made to improve the mechanical strength of the layer (JP-A-6-202354, JP-A-5-323630, etc.). However, when an electrophotographic photosensitive member having a surface layer having such a configuration is used for a long time in an apparatus to which a contact charging system is applied, the mechanical strength of the surface layer rapidly decreases after a predetermined period, and the cleaning blade In the case of performing mechanical cleaning such as the above, abrasion is greatly increased. It is considered that this is caused by strong external stress such as disconnection of the thermoplastic binder resin due to application of an AC voltage in contact charging.

Furthermore, JP-A-11-38656, JP-A-11-184106, and JP-A-11-3
Japanese Patent No. 16468 discloses a technique for imparting photoelectric characteristics and durability to an organic electronic device such as an electrophotographic photosensitive member using a charge transporting material having a hydrolyzable silyl group. However, even when these methods are used, a large-area thin film may be formed in a process of manufacturing a surface protective layer on a large number of photoconductors simultaneously in a process of manufacturing an electrophotographic photoconductor, or in a process of manufacturing an organic electroluminescence element. However, there are problems such as film formation defects such as cracks and image defects.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a sufficiently high photoelectric characteristic and a sufficiently high durability, and can be manufactured reliably and easily. And an electrophotographic photoreceptor to which the organic electronic device is applied, and an electrophotographic image forming apparatus including the electrophotographic photoreceptor and capable of obtaining a sufficiently good image quality over a long period of time, and It is an object to provide a process cartridge.

[0015]

Means for Solving the Problems As a result of extensive studies to achieve the above object, the present inventors have found that an organic electronic device having a layer containing a specific organosilicon compound has:
We have found that the quantitative ratio of monofunctional or difunctional alkoxysilane and trifunctional or tetrafunctional alkoxysilane contained in the layer affects the photoelectric properties, durability and manufacturability of organic electronic devices. . Further, as a result of further research based on such knowledge, it was found that ²⁹ Si-NM
In the R spectrum, a peak of −35 to 0 ppm attributed to the amount of monofunctional or difunctional alkoxysilane, and a peak of −100 to −40 ppm attributed to the amount of trifunctional or tetrafunctional alkoxysilane. , When the area ratio satisfies a specific condition, a sufficiently high photoelectric characteristic and a sufficiently high durability can be achieved in a well-balanced manner, and the film forming property of the layer is improved so that the production of the organic device is ensured. The present invention has been found to be easy, and the present invention has been completed.

That is, the organic electronic device of the present invention comprises:
A support, laminated on the support and having the following general formula (1): W- [D-SiR _3-a Q _a ] _b (1) (wherein W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group,
a represents an integer of 1 to 3, b is an organic electronic device and a layer containing an organic silicon compound represented by the representative) an integer of 1 to 4, ²⁹ Si-NMR of the layer Peak area of -35 to 0 ppm in spectrum and -10
The peak area of 0 to -40 ppm is represented by the following relational expression (2): 0.5 ≦ S ₁ / (S ₁ + S ₂ ) (2) (where S ₁ represents a peak area of −35 to 0 ppm,
S ₂ is characterized in that to satisfy the condition represented by representing) the peak area of -100 to-40 ppm.

Further, the electrophotographic photoreceptor of the present invention is laminated on a support and has the following general formula (1): W- [D-SiR _3-a Q _a ] _b (1) (W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. ,
a represents an integer of 1 to 3, b is an electrophotographic photoreceptor and a layer containing an organic silicon compound represented by the representative) an integer of 1 to 4, the layer ²⁹ Si- Peak area of -35 to 0 ppm in NMR spectrum and -100
The peak area of −−40 ppm is represented by the following relational expression (2): 0.5 ≦ S ₁ / (S ₁ + S ₂ ) (2) (where S ₁ represents a peak area of −35 to 0 ppm,
S ₂ is characterized in that to satisfy the condition represented by representing) the peak area of -100 to-40 ppm.

Further, the electrophotographic image forming apparatus of the present invention comprises the above electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, and an electrostatic latent image on the electrophotographic photosensitive member. An exposure device for forming an image, a developing device for developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, and transferring the toner image to a transfer material And a cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member.

Further, the process cartridge of the present invention is a charging device for charging the electrophotographic photosensitive member, and a toner image is formed by developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner. And at least one member selected from the group consisting of a cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member, and the electrophotographic photosensitive member of the present invention. It is characterized by the following.

According to the present invention, in an organic electronic device having a layer containing a specific organic silicon compound, -35 to 0 pp in a ²⁹ Si-NMR spectrum of the layer is provided.
By controlling the formation of trifunctional or tetrafunctional alkoxysilane in the layer so that the peak area of m and the peak area of -100 to -40 ppm satisfy the condition represented by the above formula (2). In addition, a sufficiently high photoelectric characteristic and a sufficiently high durability can be achieved in a well-balanced manner, and the layer can be reliably and easily formed in a manufacturing process. Therefore, when the organic electronic device of the present invention is applied to an electrophotographic photosensitive member of an electrophotographic image forming apparatus, a sufficiently high image quality can be obtained for a long period of time.

The peak area of -35 to 0 ppm in the ²⁹ Si-NMR spectrum and -10
The peak area of 0 to -40 ppm is defined as Vari
It is measured in accordance with the CP-MAS method described in anUNITY-300 instruction manual and the like. About 150 mg of a sample is ground using a mortar or the like, and filled in a zirconia sample tube (7 mmφ). Frequency 5
-35-0 p in a solid-state ²⁹ Si-NMR spectrum obtained by measuring under the conditions of 9.59 MHz, a delay time of 10.00 seconds, and a contact time of 2.5 ms.
pm and a peak area of -100 to -40 ppm.

Further, in the present invention, the layer containing the organosilicon compound represented by the general formula (1) further comprises the following general formula (3): A- [D′-SiR ′ _3-c Q ′ _c ] _n (3) wherein A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group or a siloxane group; 'Represents a divalent functional group; R' represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group; Q 'represents a hydrolyzable group; c represents an integer of 1 to 3; Represents an integer of 2 or more), and the organic silicon compound represented by the general formula (1)
0.1 to 1 part by weight of the organic silicon compound represented by
It is preferred to contain 10 parts by weight.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
In the drawings, the same or corresponding portions are denoted by the same reference characters.

The organic electronic device of the present invention comprises a support,
The following general formula (1): W- [D-SiR_3-aQ_a]_b (1) (wherein, W represents a photofunctional organic group, and D is a divalent functional group.
R represents a hydrogen atom, an alkyl group or a substituent or
Represents an unsubstituted aryl group, Q represents a hydrolyzable group,
a represents an integer of 1 to 3, b represents an integer of 1 to 4)
A layer containing an organic silicon compound represented by
Wherein the layer ²⁹In the Si-NMR spectrum
-35 to 0 ppm peak area and -100 to -40p
pm peak area and the following relational expression (2): 0.5 ≦ S₁/ (S₁+ S_Two(2) (where S₁Represents a peak area of -35 to 0 ppm,
S_TwoRepresents a peak area of -100 to -40 ppm)
It satisfies the condition expressed.

Here, the support used in the present invention is, specifically, a metal such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, platinum or the like. Plate, drum, belt, conductive polymer, conductive compounds such as indium oxide, metals such as aluminum, palladium, and gold or alloys containing these metals, or alloys containing these metals. Paper, plastic films, belts and the like. These conductive supports may be subjected to surface treatment such as anodic oxide coating treatment, thermal hydroxylation treatment, chemical treatment, coloring treatment, irregular reflection treatment (graining, etc.) as necessary, as long as they do not affect the image quality. Will be applied.

Further, in the present invention, as described above, a layer containing the organic silicon compound represented by the above formula (1) is laminated on the support. Here, the above equation (1)
In the formula, the photofunctional organic group represented by W means photoisomerization, photochromism, photoionization,
An organic group that exhibits a physical change or a physicochemical change such as light emission, nonlinear optical effect, or photoelectrochemical effect, and preferably has an aromatic ring. More preferably, W is a phthalocyanine structure, a porphyrin structure, an azobenzene structure, or a stilbene structure. , Tris (bipyridyl) -rhodium structure, azulene structure, polyene structure, nitroaniline structure, triarylamine structure, benzidine structure, arylalkane structure, aryl-substituted ethylene structure, anthracene structure, hydrazone structure, quinone structure and fluorenone structure It has one kind selected from the following. Among the organosilicon compounds having such a structure, those having photocarrier transport properties are preferably triarylamine-based compounds, benzidine-based compounds, arylalkane-based compounds, aryl-substituted ethylene-based compounds, stilbene-based compounds, and anthracene-based compounds. And at least one selected from the group consisting of hydrazone compounds, quinone compounds and fluorenone compounds; particularly preferably, W is the following general formula (4):

Embedded image (Wherein, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may be the same or different and each represents a substituted or unsubstituted aryl group, and Ar ⁵ is a substituted or unsubstituted divalent aromatic hydrocarbon. And k represents 0 or 1, and Ar ¹ , A
In r ^2, 1 to 4 pieces of Ar ^3, Ar ^4, Ar ⁵ have a bond that binds to a group represented by _{-D-SiR 3-a} Q a in the general formula (1)) It is a compound represented.

Here, in the above formula (4), Ar ¹ , Ar ² ,
The substituted or unsubstituted aryl groups represented by Ar ³ and Ar ⁴ include the following formulas (5) to (11):

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Embedded image(Where R¹Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Phenyl group, alkylphenyl group having 7 to 10 carbon atoms, charcoal
An alkoxyphenyl group having a prime number of 7 to 10 or a carbon number of 7 to
10 represents an aralkyl group;^TwoAnd R^ThreeIs water
An atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms,
Alkoxy group, phenyl group, alkoxy having 7 to 10 carbon atoms
Phenyl group, aralkyl group having 7 to 10 carbon atoms or halo
A gen group, Ar⁶Is a substituted or unsubstituted divalent fragrance
Represents a group hydrocarbon group, Z represents a divalent functional group, and s represents 1
Represents an integer of 1 to 3, and represents -DS in the above general formula (1).
iR _3-aQ_aIndicates the bonding position when the group represented by
Those having any of the structures represented by
Good. Further, Ar in the above formula (11)⁶Represented by
As a substituted or unsubstituted divalent aromatic hydrocarbon group,
The following general formula (12) or (13):

Embedded image

Embedded image (Wherein, R ⁴ and R ⁵ are a hydrogen atom and a carbon number of 1 to 1, respectively)
4 represents an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group or a halogen group having 7 to 10 carbon atoms, and t represents an integer of 1 to 3 The divalent group represented by Z in the above formula (11) is preferably a compound having the structure represented by the following formulas (14) to (21):

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Embedded image

Embedded image

Embedded image

Embedded image

Embedded image (Wherein, R ⁶ and R ⁷ are a hydrogen atom and a carbon number of 1 to 1, respectively)
An alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a halogen group;
Represents a divalent group, q and r each represent an integer of 1 to 10, and t represents an integer of 1 to 3). Furthermore,
As the divalent group represented by Z ′ in the above formula (21),
Formulas (22) to (30) below:

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Embedded image (Wherein, p represents an integer of 0 to 3).

[0028] In the above formula (1), the divalent group represented by D is _{preferably, -C n H 2n -, -} C n H 2n-2 -, - C n
H _2n- 4-(n is an integer of 1 to 15, preferably 2 to
An integer of 10), —CH ₂ —C ₆ H ₄ — or —C ₆ H
₄ -C ₆ H ₄ - a divalent hydrocarbon group represented by oxycarbonyl group (-COO-), a thio group (-S-), a an oxy group (-O-), a isocyano group (-N = CH -) Or a divalent group obtained by combining two or more of these. In addition, these divalent groups may have a substituent such as an alkyl group, a phenyl group, an alkoxy group, or an amino group on a side chain. When D is the above-mentioned preferred divalent group, appropriate flexibility is imparted to the three-dimensional inorganic vitreous network using the organosilicon compound (1), and the strength of the layer tends to be improved. .

In the above formula (1), the hydrolyzable group represented by Q means a siloxane bond (O-Si-) by hydrolysis in the curing reaction of the organosilicon compound represented by the above general formula (1). O) is a functional group capable of forming. Preferred examples of the hydrolyzable group according to the present invention include, specifically, a hydroxyl group, an alkoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, and a chloro group.
A group represented by R ′ (R ′ is an alkyl group having 2 to 15 carbon atoms or a trimethylsilyl group having 1 to 4 carbon atoms) is more preferable. When a silicon compound having such a hydrolyzable group is used, hydrolysis in the hydrolyzable group of the raw material compound (silicon compound) or the target product (photofunctional organic silicon compound) in the synthesis step is suppressed. The purity and yield of the target compound tend to be further improved. In particular, an —OR ′ group in which R ′ is a branched alkyl group having 3 to 10 carbon atoms is particularly preferable because it can be produced at lower cost.

In the organosilicon compound (1) having such a structure, Ar ¹ in the compound in which W is a substituted or unsubstituted aryl group represented by the general formula (4),
^{Ar 2, Ar 3, Ar 4} , Ar 5, D-SiR 3-a Q a following Table 1 the preferred combination of groups and integer k is represented by
3 is shown. In the table, S represents Ar ¹ , Ar ² , Ar ³ , A
-D-SiR _3-a Q _a is attached at a predetermined bonding position of r ⁴ or Ar ⁵
Represents that they are bonded.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

The organic electronic device of the present invention has sufficiently high photoelectric characteristics and sufficiently high durability, which have not been achieved by the prior art, and can be manufactured reliably and easily. As for the characteristics, the peak area ratio S ₁ / (S ₁ + S ₂ ) in the ²⁹ S-NMR spectrum of the layer containing the organosilicon compound represented by the above general formula (1) is represented by the above relational expression (2). Condition, preferably the following relational expression (3)
1): 0.6 ≦ S ₁ / (S ₁ + S ₂ ) (31) (in the formula, S ₁ represents a peak area of −35 to 0 ppm,
S ₂ represents a peak area of -100 to -40 ppm), and is achieved only by suppressing the formation of trifunctional or tetrafunctional alkoxysilane in the layer so as to satisfy the condition represented by the following formula: is there. The organic electronic device according to the present invention having such characteristics includes the following materials (a) to (c): (3): A- [D'- SiR '3-c Q' c] n (3) ( in the formula, a n-valent aliphatic hydrocarbon radical straight or branched, substituted or unsubstituted n Valent aromatic hydrocarbon group, imino group (-NH-) or siloxane group (-Si-O-)
D ′ represents a divalent functional group, R ′ represents a hydrogen atom,
An organic silicon compound represented by an alkyl group or a substituted or unsubstituted aryl group, Q ′ represents a hydrolyzable group, c represents an integer of 1 to 3, and n represents an integer of 2 or more. (B) silane coupling agent (c) hard coat agent At least one selected from the group consisting of the following is preferably used in an amount of 0.01 to 10 with respect to 1 part by weight of the organosilicon compound represented by the general formula (1). Parts by weight (more preferably 0.1 parts by weight)
To 1 part by weight).

In the above formula (3), the linear or branched n-valent aliphatic hydrocarbon group represented by A includes a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group. , A hexylene group, an octyl group and the like; Examples of the substituted or unsubstituted n-valent aromatic hydrocarbon group include a phenylene group and a diphenylethylene group. In the general formula (3), the groups represented by D ′, R ′ and Q are specifically exemplified in the description of the organic silicon compound represented by the general formula (1). And groups represented by D, R, and Q. Preferred examples of (a) the organosilicon compound (3) having such a structure are shown in Table 4 below.

[0036]

[Table 4]

As the silane coupling agent (b) used in the present invention, tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyl Trimethoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropylmethyldimethoxysilane, N-β
Trifunctional alkoxysilanes such as (aminoethyl) γ-aminopropyltriethoxysilane; difunctional alkoxysilanes such as dimethyldimethoxysilane and diphenyldimethoxysilane; and monofunctional alkoxysilanes such as trimethylmethoxysilane. Among these, it is preferable to use a trifunctional or tetrafunctional alkoxysilane because the mechanical strength of the obtained organic electronic device tends to be improved.On the other hand, a monofunctional or difunctional alkoxysilane is preferably used. The use is preferable because the flexibility and the film forming property of the obtained organic electronic device tend to be improved.

As the hard coat agent (c) used in the present invention, specifically, KP-85, X-40-
9740, X-40-2239 (all manufactured by Shin-Etsu Silicone Co., Ltd.); AY42-440, AY42-441, AY
49-208 (all manufactured by Dow Corning Toray Co., Ltd.).

Among the above (a) to (c), when (a) the organosilicon compound represented by the general formula (3) is used in combination with the organosilicon compound represented by the general formula (1), It is particularly preferable because the amount of trifunctional or tetrafunctional alkoxysilane in the layer is reliably and easily suppressed, and the photoelectric characteristics, durability, and manufacturability of the obtained organic electronic device tend to be further improved.

Further, in the present invention, a fluorine-containing compound can be blended with a raw material containing the organic silicon compound represented by the general formula (1). Specific examples of the fluorine-containing compound used in the present invention include (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane and (3,3,3-trifluoropropyl) trimethoxy. Silane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2
H, 2H-perfluoroalkyltriethoxysilane,
1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, and the like. When these fluorine-containing compounds are used, water repellency tends to be imparted to the layer laminated on the support. The compounding amount of the fluorine-containing compound is preferably 0.5 or less by weight relative to the other raw material compounds not containing fluorine. If the amount of the fluorine-containing compound exceeds the above upper limit, the film-forming properties tend to decrease.

The layer containing the organosilicon compound represented by the general formula (1) can be reliably and easily formed on a support by the following method. First, a raw material compound containing an organic silicon compound represented by the above general formula (1) is added to a predetermined organic solvent and mixed, and water and an ion exchange resin (Amberlyst 15E or the like) are added thereto to carry out hydrolysis. Do. After completion of the reaction, an insoluble component such as an ion exchange resin contained in the reaction mixture is removed by filtration or the like to obtain a coating liquid. Next, the obtained coating liquid is applied onto a support by a method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. After drying, the desired organic electronic device is obtained. Here, as the solvent used in the present invention, specifically, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, cyclohexanol; diethyl ether, dibutyl ether, dimethoxyethane, diethoxy Ethers such as ethane; aromatic solvents such as xylene and p-cymene; cellsolves such as methylcellsolve and ethylcellsolve;
And the like. Examples of the solid catalyst insoluble in a system such as an ion exchange resin used in the above hydrolysis include Amberlite 15, Amberlite 200C,
Amberlyst 15 (from Rohm and Haas), Dowex MWC-1-H, Dowex 8
8, Dowex HCR-W2 (both manufactured by Dow Chemical Company), Levatit SPC-108, Lewatit SPC
-118 (manufactured by Bayer AG), Diaion RCP
-150H (Mitsubishi Chemical Corporation), Sumikaion KC-47
0, Duolite C26-C, Duolite C-43
3. Duolite 464 (all manufactured by Sumitomo Chemical Co., Ltd.),
Cation exchange resins such as Nafion-H (manufactured by DuPont); anion exchange resins such as Amberlite IRA-400 and Amberlite IRA-45 (both manufactured by Rohm and Haas); Zr (O ₃ PCH) ₂ CH ₂ SO
Inorganic solid having a group having a protonic acid group such as ₃ H) ₂ or Th (O ₃ PCH ₂ CH ₂ COOH) ₂ bonded to the surface; containing a protonic group such as polyorganosiloxane having a sulfonic acid group Polyorganosiloxane; heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; isopolyacids such as niobate, tantalate, molybdate; silica gel, alumina, chromia, zirconia, calcium oxide (CaO), magnesium oxide (M
gO) and other complex metal oxides such as silica-alumina, silica-magnesia, silica-zirconia and zeolites; clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; lithium sulfate ( Metal sulfates such as Li ₂ SO ₄ ) and magnesium sulfate (MgSO ₄ ); metal phosphates such as zirconia phosphate and lanthanum phosphate; lithium nitrate (LiNO ₃ ), manganese nitrate (Mn (NO ₃ ) ₂ ) A metal nitrate; an inorganic solid having an amino group-containing group such as a solid obtained by reacting aminopropyltriethoxysilane on silica gel bonded to the surface; a polyamino-containing silicone such as an amino-modified silicone resin Organosiloxane, and the like. In addition to the above solid catalysts, inorganic acids such as hydrochloric acid, acetic acid, sulfuric acid, and phosphoric acid; pseudo acids, propionic acids,
Organic acids such as oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid; alkaline catalysts such as potassium hydroxide, sodium hydroxide, calcium hydroxide and ammonia; organic metals and metal alkoxides such as dibutyltin dilaurate , Dibutyltin dioctiate,
Organic tin compounds such as dibutyltin diacetate, aluminum tris (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), Metal chelates such as zirconium bis (butoxy) bis (acetylacetonate) and zirconium bis (isopropoxy) bis (acetylacetonate) and boron compounds such as boron butoxide and boric acid can be used as the catalyst.

Further, the above-mentioned hydrolysis can be carried out under conventionally known reaction conditions, and the reaction temperature is usually -30 to 100 ° C, preferably -10 to 40 ° C. The drying step of the coating liquid is usually 60 to 200.
C., preferably at 80-150.degree.

Next, a preferred embodiment of an electrophotographic photosensitive member to which the organic electronic device of the present invention is applied will be described. FIG. 1 is a schematic sectional view of the electrophotographic photosensitive member of the present invention. The electrophotographic photoreceptor 1 is a laminated type photoreceptor in which functions are separated into a charge generation layer 4 and a charge transport layer 5 in a photosensitive layer 3 laminated on a support 2. A surface protective layer 6 containing the organic silicon compound represented by (1) is provided, and an undercoat layer 7 is provided between the support 2 and the photosensitive layer 3 (charge generation layer 4). And, in the ²⁹ Si-NMR spectrum of the surface protective layer 6, -35
The peak area of ０0 ppm and the peak area of -100 to -40 ppm satisfy the above relational expression (2).

Here, as the support 2 in FIG. 1, those exemplified in the above description of the support used in the organic electronic device of the present invention can be mentioned. Support 2
Is subjected to, if necessary, the surface treatment exemplified in the description of the support used in the organic electronic device of the present invention. Further, in the present invention, it is preferable to provide an undercoat layer 7 made of a binder resin between the support 2 and the photosensitive layer 3 as shown in FIG. When the undercoat layer is provided in this manner, when the photosensitive layer 3 is charged, the charge is prevented from flowing into the photosensitive layer 3 from the support 2 and the photosensitive layer 3 is integrally bonded to the support 2. It is held, and depending on its material, light reflection of the support 2 tends to be prevented. As the binder resin used in the undercoat layer of the present invention,
Specifically, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polyurethane resin, melamine resin, benzoguanamine resin, polyimide resin, polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, methacrylic resin, vinylidene chloride resin, Polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound , A titanyl chelate compound, a titanyl alkoxide compound, an organic titanyl compound, a silane coupling agent, and the like. These materials may be used alone. , It may be used as a mixture of two or more. Further, in the present invention, fine particles made of an inorganic material such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin can be blended in the undercoat layer 7.

As a method for forming the undercoat layer 7, a conventionally known method can be used. Specifically, a coating liquid containing a binder resin and an organic solvent is prepared, and the obtained coating liquid is prepared. The support liquid is applied to the support 2 by a method such as blade coating, Meyer bar coating, spray coating, dip coating, bead coating, air knife coating, or curtain coating.
Coating on top and drying. Here, specific examples of the organic solvent used in the step of forming the undercoat layer include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methylcellosolve, ethylcellosolve, acetone, and methylethylketone. , Cyclohexanone, chlorobenzene, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform and the like. These may be used alone or as a mixture of two or more. The thickness of the undercoat layer thus obtained is preferably 0.01 to 10 μm, more preferably 0.05 to 2 μm. When the thickness of the undercoat layer is less than 0.01 μm, characteristics such as the ability of preventing the charge from flowing from the support 2 to the photosensitive layer 3 and the adhesion between the support 2 and the photosensitive layer 3 tend to be insufficient. Yes, on the other hand,
If it exceeds 0 μm, the electrophotographic properties tend to be reduced.

The charge generation layer 4 usually contains a charge generation material and a binder resin. Here, as the charge generating material used in the present invention, specifically, azo pigments, quinone pigments, perylene pigments, indigo pigments, thioindigo pigments, bisbenzimidazole pigments, phthalocyanine pigments, Organic pigments such as quinacridone-based pigments, quinoline-based pigments, lake-based pigments, azo lake-based pigments, anthraquinone-based pigments, oxazine-based pigments, dioxazine-based pigments, and triphenylmethane-based pigments; And dyes such as triallylmethane dye, xanthene dye, thiazine dye and cyanine dye; inorganic materials such as amorphous silicon, amorphous selenium, tellurium, selenium-tellurium alloy, cadmium sulfide, antimony sulfide, zinc oxide and zinc sulfide , Etc., It is, sensitivity, preferable from the viewpoint of electric stability and photochemical stability using condensed aromatic pigments among these, a perylene pigment or azo pigment.

Examples of the binder resin used for the charge generation layer 4 include polyvinyl acetal resins (polyvinyl butyral resin, polyvinyl formal resin, partially acetalized polyvinyl resin in which a part of butyral is modified with formal, acetoacetal, or the like). Acetal resin), polyamide resin, polyester resin, modified ether type polyester resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, silicone Resins, phenolic resins, phenoxy resins, melamine resins, benzoguanamine resins, urea resins, polyurethane resins, poly-N-vinylcarbazole resins, polyvinylanthracene resins, polyvinylpyrene, etc. It is below. Among these, when a polyvinyl acetal-based resin, a vinyl chloride-vinyl acetate-based copolymer, a phenoxy resin or a modified ether-type polyester resin is used, the dispersibility of the charge generating material is improved, the aggregation thereof is prevented, and stable for a long time. A coating liquid tends to be obtained. When such a coating liquid is used, the charge generation layer is formed into a uniform film, and the electrical characteristics are improved. As a result, the occurrence of image quality defects tends to be suppressed. In the present invention, the charge generation layer 5 contains a phenolic compound,
Antioxidants such as sulfur compounds, phosphorus compounds and amine compounds, bis (dithiobenzyl) nickel, di-n-
A deactivator, such as nickel butylthiocarbamate, may be added.

As a method for forming the charge generation layer 4, a conventionally known method can be used. Specifically, a coating solution containing the charge generation material and the binder resin is coated by a blade coating method. And a method of applying to a support by a method such as a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method, followed by drying. Here, examples of the organic solvent used in the step of forming the charge generation layer include the organic solvents exemplified in the description of the method of forming the undercoat layer 7. The mixing ratio of the charge generation material to the binder resin is preferably 5: 1 to 1: 2 (volume ratio). Further, the thickness of the charge generation layer thus obtained is preferably 0.01
When the thickness of the charge generation layer is less than the lower limit, it tends to be difficult to form the charge generation layer uniformly, while the upper limit is not more than 0.1 μm. When the ratio exceeds the above range, the electrophotographic properties tend to decrease.

The charge transport layer 5 usually contains a low molecular charge transport material and a binder resin or a charge transporting polymer, and optionally contains additives such as a crosslinking agent and inorganic fine particles. It is. Specific examples of the low-molecular charge transport material used in the present invention include pyrene compounds, carbazole compounds, hydrazone compounds, oxazole compounds, oxadiazole compounds, pyrazoline compounds, arylamine compounds, Arylmethane-based compounds, benzidine-based compounds, thiazole-based compounds, stilbene-based compounds, butadiene-based compounds and the like; specific examples of the charge-transporting polymer include the organosilicon compounds represented by the general formula (1). Cured product, poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene,
Examples include polyvinyl acridine, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, triphenylmethane polymer, and polysilane. Among these, it is preferable to use a cured product composed of the organic silicon compound represented by the general formula (1) because durability tends to be improved while maintaining the photoelectric characteristics of the charge transport layer at a high level. When a mobility is used, a triphenylamine compound, a triphenylmethane compound, or a benzidine compound is preferable because stability and transparency to light tend to be improved.

The binder resin used as the material of the charge transport layer 5 is preferably a high polymer capable of forming an electrically insulating film. Specifically, polycarbonate, polyester, methacrylic resin, acrylic resin resin,
Polyvinyl chloride, polyvinylidene chloride, polystyrene,
Polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile polymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-
Maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal,
Polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxy-methyl cellulose, vinylidene chloride-based polymer latex, polyurethane and the like are preferable. Among these, use of polycarbonate, polyester, methacrylic resin, and acrylic resin is particularly preferable because compatibility with the charge transporting material, solubility in a solvent, and mechanical strength tend to be improved. In addition, these binder resins may be used alone or as a mixture of two or more.

Further, in the present invention, the charge transport layer 5
Additives such as a plasticizer, a surface modifier, an antioxidant, and a photo-deterioration agent can be added to the mixture. As the plasticizer used in the present invention, specifically, biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, Various fluorohydrocarbons; antioxidants, specifically, phenolic compounds, sulfur compounds, phosphorus compounds, amine compounds, etc .; photodeterioration agents, specifically, benzotriazole compounds Benzophenone compounds, hindered amine compounds and the like.

As a method for forming the charge transport layer 5, a conventionally known method can be used. When the charge transporting material is a low molecular compound, the charge transporting material, a coating liquid containing a binder resin and an organic solvent, and in the case of a charge transporting polymer, a coating liquid containing a charge transporting polymer and an organic solvent, respectively. The prepared coating solution is applied to the support by a method such as blade coating, Meyer bar coating, spray coating, dip coating, bead coating, air knife coating, curtain coating, etc. And a method of drying. Here, specific examples of the organic solvent used in the step of forming the charge transport layer 5 include the organic solvents exemplified in the description of the method of forming the undercoat layer 7.
The thickness of the charge transport layer thus obtained is preferably 5 to 50 μm, more preferably 10 to 40 μm.
μm. When the thickness of the charge transport layer is less than 5 μm, the chargeability tends to be insufficient, while the thickness is 50 μm.
When the ratio exceeds, the electrophotographic properties tend to be remarkably reduced.

In the electrophotographic photosensitive member of the present invention, FIG.
It is preferable to provide a surface protective layer 6 containing the organic silicon compound represented by the above general formula (1) on the photosensitive layer 2 as shown in FIG. Thus, when the surface protective layer containing the organosilicon compound (1) is provided, the photoconductor surface tends to have sufficiently high durability while maintaining the photoelectric characteristics at a high level. When the surface protective layer 6 further contains a lubricant or inorganic fine particles in addition to the organic silicon compound (1), the lubricity, the adhesion of contaminants, and the mechanical strength of the surface protective layer 6 are improved. And a longer life electrophotographic photoreceptor tends to be obtained. Here, examples of the lubricant used in the present invention include silicone oil and fluorine-based silane coupling agents, and examples of the inorganic fine particles include silica-containing fine particles such as silica fine particles and silicone fine particles;
Fluorine-containing fine particles such as fine particles of ethylene tetrafluoride, fine particles of ethylene trifluoride, fine particles of propylene hexafluoride and fine particles of vinyl fluoride; ZnO-Al ₂ O ₃ , SnO ₂ -S
₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , MgO—
_{Al 2 O 3, FeO-TiO} 2, TiO 2, SnO 2, In 2
Fine particles made of semiconductive metal oxides such as O ₃ , ZnO, and MgO, or fine particles obtained by copolymerizing a polymerizable monomer having a hydroxyl group with a fluororesin (Proceedings of the 8th Polymer Material Forum, p89), among which colloidal silica or silicone fine particles are preferably used.

Here, when the silica fine particles according to the present invention are blended in the surface protective layer 6, commercially available colloidal silica can be used.
0 nm, preferably 10-30 nm silica fine particles,
An aqueous dispersion dispersed in an acidic or alkaline aqueous solution, or an aqueous dispersion dispersed in an organic solvent such as alcohol, ketone, or ester is suitably used. The content of the silica fine particles in the surface protective layer 6 is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, based on the total solid content in the surface protective layer 6. When the solid content of the silica fine particles in the surface protective layer 6 is within the above-described preferred range, the film-forming properties, electrical characteristics, and mechanical strength tend to be improved.

Further, the silicone fine particles according to the present invention are selected from the group consisting of silicone resin particles, silicone rubber particles and silicone surface-treated silica particles.
It is preferably a seed, the shape of which is spherical, and an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm. Such silicone fine particles are chemically inert, are small-diameter particles excellent in dispersibility in resin, and have a low content required for obtaining sufficient properties, so that they do not hinder the crosslinking reaction. The surface properties of the electrophotographic photosensitive member can be improved. That is, while being uniformly dispersed in a strong crosslinked structure, the lubricity and water repellency of the electrophotographic photoreceptor surface can be improved, and good abrasion resistance and contamination resistance can be maintained over a long period of time. it can. In the electrophotographic photoreceptor of the present invention, the content of the silicone fine particles in the outermost surface layer is 0.1% based on the total solid content of the surface protective layer.
It is preferably from 1 to 20% by weight, more preferably from 0.5 to 10% by weight.

As a method for forming the surface protective layer 6, a conventionally known method can be used, and specifically, a coating solution containing the organosilicon compound represented by the above general formula (1) Is prepared, and the obtained coating liquid is subjected to a blade coating method,
Examples thereof include a method of applying the composition on a support by a method such as a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method, followed by drying. Here, the organic solvent used in the step of forming the surface protective layer 6 can sufficiently dissolve the raw material compound constituting the surface protective layer and does not adversely affect the lower charge transport layer 5. Are preferred. Specific examples of such organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and cyclohexanol; ethers such as diethyl ether, dibutyl ether, dimethoxyethane, and diethoxyethane. Xylene,
Aromatic solvents such as p-cymene, and cellsolves such as methylcellosolve and ethylcellosolve are preferable. Among them, alcohols having a boiling point of 60 to 150 ° C. are preferable in terms of film-forming properties and storage stability of the coating solution. Is particularly preferred. The thickness of the surface protective layer thus obtained is preferably 0.1 to 10 μm, more preferably 0.5 to 7 μm.
m. If the thickness of the surface protective layer is less than 0.1 μm, the durability tends to be insufficient, while the thickness is 10 μm.
If it exceeds m, the electrophotographic properties tend to decrease.

The charge transport layer 5 contains the organic silicon compound represented by the above general formula (1) as a charge transport material, and the peak area ratio of the ²⁹ Si-NMR spectrum is determined by the above relational formula (2). When the conditions described are satisfied, the charge transport layer 5 may be used as the outermost layer instead of providing the surface protective layer 6. FIG. 1 shows an example of a laminated electrophotographic photosensitive member, but instead of the laminated photosensitive layer 3 in FIG. 1, a single layer type photosensitive material containing a charge generation material and a charge transport material in the same layer. Photosensitive layers may be laminated.

As described above, by using the electrophotographic photosensitive member of the present invention having sufficiently high photoelectric characteristics (electrophotographic characteristics) and sufficiently high durability, charging, image input (exposure), development, transfer, In an electrophotographic image forming process including steps such as fixing and cleaning, a high level of image quality can be obtained for a long period of time.

FIG. 2 shows a preferred embodiment of the electrophotographic image forming apparatus of the present invention. In the electrophotographic image forming apparatus shown in FIG. 2, a drum-shaped electrophotographic photosensitive member 1 having a laminated structure shown in FIG.
Is rotationally driven around the support 8 at a predetermined rotational speed in the direction of the arrow. In this rotation process, the photosensitive member 1 is contacted by the contact charging member 10 supplied with a voltage from the power supply 9.
Is uniformly charged at a predetermined positive or negative potential on its peripheral surface.
Here, as the contact charging member 10, a rubber-like roll provided with conductivity such as BCR is preferably used. Other methods for charging the photoreceptor 1 include a corona discharge method and the like, but charging by a contact charging method is preferable in that ozone is hardly generated.

Next, the photoreceptor 1 is subjected to light image exposure by the image input device (exposure device) 11, whereby an electrostatic latent image corresponding to the exposed image is formed on the peripheral surface. After that, a toner image is formed by attaching toner to the electrostatic latent image by the developing device 12, and the toner image is transferred to the transfer material P by the transfer device 13. The transfer material P after the transfer of the toner image undergoes image fixing by the image fixing device 14 and is printed out as a copy. After the transfer process, the photoreceptor 1 is cleaned by the cleaning device 15 to remove the toner remaining on the peripheral surface thereof, and then is discharged by the discharger 16 to be repeatedly used for image formation.

As described above, the electrophotographic photosensitive member 1 has a sufficiently high photoelectric characteristic and a sufficiently high durability in a well-balanced manner. Such an electrophotographic photosensitive member is used in an electrophotographic image forming apparatus. By doing so, it is possible to maintain a high level of print quality for a long period of time.

Further, in the present invention, the use of a process cartridge including an electrophotographic photosensitive member and one selected from the group consisting of a charging device, a developing device and a cleaning device is advantageous in the electrophotographic image forming apparatus. It is preferable in that the attachment and detachment of the electrophotographic photosensitive member and the like can be easily performed, and the efficiency of replacement work of these components can be improved.

As a preferred embodiment of the organic electronic device of the present invention, an organic electroluminescent element (organic EL element) shown in FIGS. 3 and 4 can be exemplified.

In FIG. 3, a transparent electrode 18, a hole transport layer 19 containing an organosilicon compound represented by the above general formula (1), and a light emitting layer 20 are formed on a transparent insulating substrate 17.
And the back electrode 21 are sequentially laminated.

In FIG. 4, the transparent insulating substrate 1
A transparent electrode 18, a light-emitting layer 22 having a carrier transport function containing an organosilicon compound represented by the above general formula (1), and a back electrode 21 are sequentially laminated on 7.

Here, the transparent insulating substrate according to the present invention is preferably transparent in order to extract light emission, and a glass, plastic film or the like is used as a material thereof.

Further, the transparent electrode according to the present invention is preferably transparent to extract light emission similarly to the transparent insulating substrate, and preferably has a large work function for performing hole injection. Examples of the transparent electrode according to the present invention include indium tin oxide (ITO) and tin oxide (NE).
SA), an oxide film such as indium oxide or zinc oxide, or gold, platinum, or palladium deposited or sputtered can be used.

The layer containing the organosilicon compound represented by the above general formula (1) according to the present invention acts as the hole transport layer 19 in the organic EL device of FIG. 3, and on the other hand, in the organic EL device of FIG. Acts as a light emitting layer 22 having a carrier transport function.

When the organic EL device has the layer configuration shown in FIG. 3, the hole transport layer 19 may be composed of the organosilicon compound represented by the general formula (1) alone, but the hole transport layer 19 controls the hole mobility. In order to achieve this, a tetraphenylenediamine derivative may be dispersed in the range of 1 to 50% by weight. Further, other general-purpose resins may be mixed.

In FIG. 3, as the light emitting material of the light emitting layer 20, a compound having a high fluorescence quantum yield in a solid state is used. Here, when the light emitting material is a low molecular weight organic compound, a good thin film can be formed by applying a vacuum evaporation method or a solution or dispersion containing the light emitting material and a binder resin and drying. That is the condition. Examples of such low-molecular organic compounds include chelating organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives,
It is preferable to use coumarin derivatives, styrylarylene derivatives, silole derivatives, oxazole derivatives, oxathiazole derivatives or oxadiazole derivatives, and the following formulas (IV-1) to (IV-12):

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Embedded image It is more preferable to use the compound represented by

When the light emitting material of the light emitting layer 20 according to the present invention is a polymer compound, it is required that a good thin film can be formed by applying and drying a solution or dispersion containing the light emitting material. is there. As such a high molecular compound, a polyparaphenylene derivative, a polyparaphenylenevinylene derivative, a polythiophene derivative or a polyacetylene derivative is preferably used.
-13) to (IV-15):

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Embedded image [In the above formulas (IV-13) to (IV-15), n is an integer of 1 or more (preferably 1 to 20, more preferably 1 to 10).
X is an integer of 1 or more (preferably 5 to 1000
0, and more preferably 10 to 1000)].

For the purpose of improving the durability and luminous efficiency of the organic EL device, the above-mentioned luminescent material may be doped with a dye compound different from the luminescent material as a guest material. Examples of the method of doping the dye compound include a method of co-evaporating the dye compound in the step of forming the light emitting layer by vacuum evaporation, a method of applying a solution or dispersion, and a step of mixing the dye compound in the solution or dispersion in the step of forming the light emitting layer by drying. And the like. Here, the ratio of the dye compound doped in the light emitting layer is usually 0.001.
-40% by weight, preferably 0.001-10% by weight. As the dye compound used in the present invention, an organic compound which has good compatibility with the light emitting material and which does not hinder favorable film formation of the light emitting layer is preferable.
It is preferable to use MC derivative, quinacudrine derivative, rubrene derivative or porphyrin, and the following formula (V-
1) to (V-4):

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Embedded image It is more preferable to use the compound represented by

Further, as a light emitting material, a light emitting layer capable of forming a thin film of a light emitting layer by vacuum deposition, coating of a solution or dispersion, and drying, but not obtaining a good thin film,
When using a material that does not show clear electron transport properties,
For the purpose of improving the durability and luminous efficiency of the organic EL element, an electron transport layer may be inserted between the light emitting layer 20 and the back electrode 21. As the electron transporting material used for such an electron transporting layer, it is preferable to use an organic compound capable of forming a good thin film by a vacuum deposition method. Specifically, oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone It is preferable to use a derivative, an oxide derivative at the time of thiopyran, or a fluorenylidenemethane derivative, and the following formulas (VI-1) to (VI-3):

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Embedded image It is more preferable to use the compound represented by

When the organic EL device has the layer structure shown in FIG. 4, the light emitting layer 22 is formed by dispersing a light emitting material at least in a proportion of 50% by weight or less in the organosilicon compound represented by the general formula (1). The compound represented by the above formulas (IV-1) to (IV-15) is preferably used as the light emitting material. Here, in order to adjust the balance between holes and electrons injected into the organic EL element, an electron transporting material may be further dispersed by 10 to 50% by weight,
Alternatively, an electron transport layer made of an electron transport material may be inserted between the light emitting layer 22 and the back electrode 21. As the electron transporting material used in the electron transporting layer according to the present invention, it is preferable to use an organic compound that does not show strong electron interaction with the organosilicon compound represented by the general formula (1),
Specifically, the following formula (VII):

Embedded image It is preferable to use a compound represented by the formula: Further, in the present invention, similarly, an appropriate amount of a tetraphenylenediamine derivative may be simultaneously dispersed and used in order to adjust the hole mobility. Further, in the present invention, the light emitting layer 22 may be doped with a dye compound different from the light emitting material.

As the back electrode 21, it is preferable to use a metal which can be vacuum-deposited and has a small work function for performing electron injection. Specifically, magnesium, aluminum, silver, indium or an alloy thereof is used. Preferably, it is used.

In the organic EL device according to the present invention, the hole transport layer 19 or the light emitting layer 22 may be composed of the organosilicon compound represented by the general formula (1) alone or the organosilicon compound represented by the general formula (1) A compound, a light emitting material, and, if necessary, an electron transporting material and a hole (hole) transporting material are dissolved or dispersed in an organic solvent, and a spin coating method is performed on the transparent electrode using the obtained coating solution, It can be obtained by forming a film by a dip method or the like. Here, the thicknesses of the hole transport layer and the light emitting layer according to the present invention are each preferably 0.03 to 0.2 μm. Further, the dispersion state of the light emitting material in these layers may be any of a molecular dispersion state and a fine particle dispersion state. When the dispersion state of the light emitting material is a molecular dispersion state, an organosilicon compound represented by the above general formula (1);
It is necessary to use a common solvent of the light emitting material, the electron transporting material and the hole transporting material as a dispersion solvent. On the other hand, when the light emitting material is dispersed in a fine particle state, the dispersibility of the light emitting material and the above general formula ( The solubility of the organosilicon compound, the electron transporting material and the hole transporting material represented by 1),
It is necessary to select a dispersion solvent in consideration of the above. In addition, when the dispersion state of the light emitting material is a fine particle dispersion state, a ball mill, a sand mill, a paint shaker, an attritor,
A homogenizer, an ultrasonic wave or the like can be used.

A light emitting material, an electron transporting material, or an electron transporting material is formed on the thus formed layer containing the organic silicon compound represented by the general formula (1), depending on the layer structure of each organic EL element. Back electrode is formed by vacuum evaporation method,
The organic EL device according to the present invention can be obtained. Here, in the present invention, the thickness of each of the light emitting layer and the electron transport layer having an electron transport ability is preferably 0.1 μm or less, and particularly preferably 0.03 to 0.08 μm. Further, the organic EL device according to the present invention comprises:
For example, at a current density of 1 to 2 at 4 to 20 V between a pair of electrodes.
Light emission can be achieved by applying a direct current voltage of 00 mA / cm ² .

[0078]

EXAMPLES The present invention will now be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. In the following examples,
Among the organosilicon compounds represented by the general formula (4), those having a combination of the functional groups shown in the above Tables 1 to 3 are denoted by the corresponding compound numbers, and “Exemplified compound [N
o. 28] ". Similarly, among the organic compounds represented by the general formula (3), those having the structure shown in Table 4 above are assigned with corresponding compound numbers, and are referred to as “exemplary compound [III-6]” or the like. And

(Production of Electrophotographic Photoreceptor) Example 1 Sixteen electrophotographic photoreceptors were simultaneously produced according to the following procedures.

First, an outer diameter of 30 m subjected to honing treatment
100 parts by weight of a zirconium compound (trade name: Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and a silane compound (trade name: A110)
0, manufactured by Nippon Unicar) 10 parts by weight, a solution consisting of 400 parts by weight of isopropanol and 200 parts by weight of butanol was applied by dip coating, and dried by heating at 150 ° C. for 10 minutes.
An undercoat layer of 0.1 μm was formed.

Next, the charge generation material has a Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum of 7.4.
Chlorogallium phthalocyanine crystal 10 having strong diffraction peaks at °, 16.6 °, 25.5 ° and 28.3 °
10 parts by weight of a polyvinyl butyral resin (trade name: ESLEC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 1000 parts by weight of butyl acetate were mixed together with glass beads and subjected to a dispersion treatment for 1 hour using a paint shaker. The coating solution thus obtained is applied onto the undercoat layer by dip coating, and dried by heating at 100 ° C. for 10 minutes.
A μm charge generation layer was formed.

Further, the following structural formula (32):

Embedded image 20 parts by weight of a benzidine compound represented by the following formula and a bisphenol (Z) polycarbonate resin (viscosity average molecular weight:
4.4 × 10 ⁴ ) 30 parts by weight of monochlorobenzene 15
A coating solution obtained by dissolving in a mixed solvent of 0 parts by weight and 150 parts by weight of tetrahydrofuran is dip-coated on the charge generation layer, and dried by heating at 115 ° C. for 1 hour to form a charge transport layer of 20 μm. did.

Further, the exemplified compound [No. 28], 20 parts by weight of Exemplified Compound [III-6], 20 parts by weight of isopropyl alcohol (IPA), and 20 parts by weight of methanol were collected and mixed well. Further, 2 parts by weight of ion exchange resin (Amberlyst 15E), 24 parts of distilled water
The mixture was stirred at room temperature for 10 hours, and then subjected to thin layer chromatography (TLC, developing solvent: hexane / ethyl acetate = 3/1, adsorbent: silica gel) to give the exemplified compound [No. 28] was confirmed. Thereafter, the ion exchange resin and a small amount of precipitate in the reaction solution were removed by filtration,
A coating liquid was prepared by adding and dissolving 0.5 parts by weight of aluminum trisaceteracetonate and 1 part by weight of acetylacetone, and dip-coating the obtained coating liquid on the above-described charge transport layer, and then applying the solution at 120 ° C. For 1 hour to form a 5 μm surface protective layer to obtain the intended electrophotographic photoreceptor.

The electrophotographic photoreceptor 1 thus prepared
All six samples had good surface conditions, and no film formation defects such as cracks and uneven drying were observed.

Further, the surface protective layer was peeled off from the thus obtained electrophotographic photoreceptor using an adhesive tape not containing silicon, and about 150 mg of the peeled material was finely ground in a mortar to prepare a sample tube made of zirconia. (7 mmφ) and the ²⁹ Si-NMR spectrum was measured. Note that ²⁹
The measurement of the Si-NMR spectrum is performed by UN manufactured by Varian.
Using ITY-300, the following conditions: Frequency: 59.59 MHz Delay time: 10.00 seconds Contact time: 2.5 milliseconds Number of integrations: 10000 times Measurement temperature: 25 ° C. Sample rotation speed: Measured at 4000 ± 500 rpm did. The ²⁹ Si-NMR spectrum obtained 4, respectively peaks were calculated based on the ²⁹ Si-NMR spectra obtained area ratio S ₁ / a (S ₁ + S ₂₎ Table 5, the.

Example 2 The exemplified compound [No. 28] Exemplified compound [No. 29], and 16 electrophotographic photoreceptors were simultaneously prepared in the same manner as in Example 1 except that 25 parts by weight of Exemplified Compound [III-6] was used, and observation of the surface state and ²⁹ Si-NMR
The spectrum was measured.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Example 3 The exemplified compound [No. 28] Exemplified compound [No. 37] An electrophotographic photoreceptor 1 was prepared in the same manner as in Example 1 except that 20 parts by weight was used.
At the same time to produce six to, the surface state observation and ²⁹ Si-N
An MR spectrum was measured.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Example 4 The exemplified compound [No. 28] Exemplified compound [No. 29] 25 parts by weight and the exemplified compound [III-6] 30 parts by weight instead of the exemplified compound [I
II-4] 5 parts by weight and Exemplified Compound [III-6] 20 parts by weight were used, respectively, and 16 electrophotographic photoreceptors were simultaneously prepared in the same manner as in Example 1 to observe the surface condition and to observe the surface condition. ^{A 29} Si-NMR spectrum was measured.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Example 5 The exemplified compound [No. 28] Exemplified compound [No. 29] 25 parts by weight and the exemplified compound [III-6] 30 parts by weight instead of the exemplified compound [I
II-4] 15 parts by weight and exemplified compound [III-6] 10
In the same manner as in Example 1 except that the respective parts by weight were used, 16 electrophotographic photosensitive members were simultaneously produced, and the observation of the surface state and the measurement of ²⁹ Si-NMR spectrum were performed.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Example 6 The exemplified compound [No. 28] Exemplified compound [No. 29] 25 parts by weight and the exemplified compound [III-6] 30 parts by weight instead of the exemplified compound [I
II-4] 10 parts by weight and exemplified compound [III-6] 15
In the same manner as in Example 1 except that the respective parts by weight were used, 16 electrophotographic photosensitive members were simultaneously produced, and the observation of the surface state and the measurement of ²⁹ Si-NMR spectrum were performed.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Example 7 The exemplified compound [No. 28] Exemplified compound [No. 29] 25 parts by weight and the exemplified compound [III-6] 30 parts by weight instead of the exemplified compound [I
II-6] 15 parts by weight and silicone-based fine particles (AER
OSIL R812) Sixteen electrophotographic photoreceptors were simultaneously prepared in the same manner as in Example 1 except that 10 parts by weight of OSIL R812) were used, and the surface state was observed and ²⁹ Si-NMR was used.
The spectrum was measured.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Comparative Example 1 Sixteen electrophotographic photosensitive members were simultaneously produced in the same manner as in Example 1 except that the surface protective layer was not provided, and the observation of the surface state and the measurement of the ²⁹ Si-NMR spectrum were performed. A measurement was made.

The surface condition of the obtained electrophotographic photosensitive member and
Peak area of ²⁹ Si-NMR spectral ratio S ₁ /
Table 5 shows (S ₁ + S ₂ ).

Comparative Example 2 The procedure up to the preparation of the charge transporting layer was carried out in the same manner as in Example 1.
o. 28] Exemplified compound [No. 2
Example 9 except that 25 parts by weight of Exemplified Compound [III-6] and 5 parts by weight of Exemplified Compound [III-6] were used instead of 30 parts by weight of Exemplified Compound [III-6]. When 16 electrophotographic photoreceptors were simultaneously produced in the same manner as in No. 1, wrinkle-like film formation defects were particularly observed on the two photoreceptors arranged near the hot air jet used for drying.

Table 5 shows the surface condition of the electrophotographic photosensitive member thus obtained and the peak area ratio S ₁ / (S ₁ + S ₂ ) in the ²⁹ Si-NMR spectrum.

Comparative Example 3 The procedure up to the preparation of the charge transport layer was carried out in the same manner as in Example 1.
o. 28] Exemplified compound [No. 2
9] and 25 parts by weight of Exemplified Compound [III-4] in place of 30 parts by weight of Exemplified Compound [III-6], in the same manner as in Example 1, except that 25 parts by weight of Exemplified Compound [III-4] were used. When the books were prepared at the same time, a wrinkle-like film formation defect was observed particularly on the four photoconductors arranged near the hot air outlet used for drying.

Table 5 shows the surface condition of the electrophotographic photosensitive member thus obtained and the peak area ratio S ₁ / (S ₁ + S ₂ ) in the ²⁹ Si-NMR spectrum.

(Printing Test) An electrophotographic image forming apparatus (Laser Press 4161II) having the structure shown in FIG. 1 was obtained by using each of the electrophotographic photosensitive members of Examples 1 to 7 and Comparative Examples 1 to 3 thus obtained. Was modified, and each device was subjected to normal temperature and normal humidity (about 20 ° C., 4
A print test (print paper: acidic paper) of 50,000 sheets was performed under two conditions of 0% RH and high temperature and high humidity (about 29 ° C., 85% RH), and the image quality of the copy and the surface condition of the photoreceptor were evaluated. . Table 5 shows the results. In the evaluation of the image quality, the presence or absence of image quality defects was observed for the first and 50,000th copies, and in the evaluation of the surface state of the photoreceptor, the presence or absence of scratches and attached matter was observed.

[0105]

[Table 5]

As shown in Table 5, in Examples 1 to 7, all 16 electrophotographic photosensitive members produced at the same time had good surface conditions without wrinkles or the like. In all of the print tests using these electrophotographic photoreceptors, good image quality can be obtained even on the 50,000th copy, and the photoreceptor surface after the test is free of scratches and deposits. I was not able to admit.

In contrast, when the electrophotographic photosensitive member of Comparative Example 1 was used, image quality defects in the 50,000th copy and generation of scratches on the photosensitive member surface after the test were observed. Also, in Comparative Examples 2 and 3, wrinkles occurred in some of the 16 electrophotographic photosensitive members manufactured at the same time, and when these electrophotographic photosensitive members were used, a copy was obtained from the beginning of the print test. Image quality defects were observed, and deposits were observed on the photoreceptor surface after the test.

[0108]

As described above, according to the present invention,
An organic electronic device having sufficiently high photoelectric characteristics and sufficiently high durability and capable of being reliably and easily manufactured is obtained. By applying the organic electronic device of the present invention to an electrophotographic photoreceptor and using it in an electrophotographic image forming apparatus, it is possible to obtain sufficiently good image quality over a long period of time.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a preferred embodiment of an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic configuration diagram showing a preferred embodiment of the electrophotographic image forming apparatus of the present invention.

FIG. 3 is a schematic configuration diagram showing a preferred embodiment of an organic electroluminescence element according to the present invention.

FIG. 4 is a schematic configuration diagram showing a preferred embodiment of an organic electroluminescence element according to the present invention.

FIG. 5 is a graph showing a ²⁹ Si-NMR spectrum of a surface protective layer of the electrophotographic photosensitive member obtained in Example 1.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photoreceptor, 2 ... Conductive support, 3 ... Photosensitive layer,
4: charge generation layer, 5: charge transport layer, 6: surface protective layer, 7
... undercoat layer, 8 ... support, 9 ... power supply, 10 ... charging member,
11 image input device, 12 developing device, 13 transfer device, 14 image fixing device, 15 cleaning device, 16
... static eliminator, 17 ... transparent insulating substrate, 18 ... transparent electrode, 1
9: hole transport layer, 20: light emitting layer, 21: back electrode, 2
2. Light-emitting layer having carrier transport ability.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuhiro Koseki 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture F-Xerox Co., Ltd. F-term (reference) 2H068 AA03 BA58 BB44 FA27

Claims (6)

[Claims] 1. A support, which is laminated on the support and has the following general formula (1): W- [D-SiR _3-a Q _a ] _b (1) (where W is optical functionality Represents an organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group,
a represents an integer of 1 to 3, b represents an integer of 1 to 4), and a layer containing an organosilicon compound represented by the formula ( ^29): -35 to 0 in the spectrum
The peak area of ppm and the peak area of -100 to -40 ppm are expressed by the following relational expression (2): 0.5 ≦ S ₁ / (S ₁ + S ₂ ) (2) (where S ₁ is −35 to 0 ppm) Represents the peak area,
The organic electronic device S ₂ is characterized by satisfying the condition represented by representing) the peak area of -100 to-40 ppm. 2. The layer containing the organosilicon compound represented by the general formula (1) further comprises a layer represented by the following general formula (3): A- [D′-SiR ′ _3-c Q ′ _c ] _n (3 Wherein A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group or a siloxane group, and D ′ represents a divalent Represents a functional group, R ′ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q ′ represents a hydrolyzable group, c represents an integer of 1 to 3, and n represents an integer of 2 or more. Represents the organosilicon compound represented by the general formula (1)
0.1 to 1 part by weight of the organic silicon compound represented by
The organic electronic device according to claim 1, wherein the content is 10 parts by weight. 3. A support, which is laminated on the support and has the following general formula (1): W- [D-SiR _3-a Q _a ] _b (1) (where W is optical functionality Represents an organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group,
a represents an integer of 1 to 3, b is an electrophotographic photoreceptor and a layer containing an organic silicon compound represented by the representative) an integer of 1 to 4, the layer ²⁹ Si- -35 to 0 in NMR spectrum
The peak area of ppm and the peak area of -100 to -40 ppm are expressed by the following relational expression (2): 0.5 ≦ S ₁ / (S ₁ + S ₂ ) (2) (where S ₁ is −35 to 0 ppm) Represents the peak area,
The electrophotographic photosensitive member S ₂ is characterized by satisfying the condition represented by representing) the peak area of -100 to-40 ppm. 4. The layer containing an organosilicon compound represented by the general formula (1) further comprises a compound represented by the following general formula (3): A- [D′-SiR ′ _3-c Q ′ _c ] _n (3 Wherein A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group or a siloxane group, and D ′ represents a divalent Represents a functional group, R ′ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q ′ represents a hydrolyzable group, c represents an integer of 1 to 3, and n represents an integer of 2 or more. Represents the organosilicon compound represented by the general formula (1)
0.1 to 1 part by weight of the organic silicon compound represented by
The electrophotographic photoreceptor according to claim 3, wherein the electrophotographic photoreceptor is contained in an amount of 10 parts by weight. 5. An electrophotographic photoreceptor according to claim 3 or 4, a charging device for charging the electrophotographic photoreceptor, and an exposure for forming an electrostatic latent image on the electrophotographic photoreceptor. A developing device for developing an electrostatic latent image formed on the electrophotographic photoreceptor with toner to form a toner image; a transfer device for transferring the toner image to a transfer material; An electrophotographic image forming apparatus, comprising: a cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member. 6. A charging device for charging the electrophotographic photosensitive member, a developing device for developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, and A process comprising: at least one selected from the group consisting of a cleaning device for removing toner remaining on the surface of an electrophotographic photosensitive member; and the electrophotographic photosensitive member according to claim 3 or 4. cartridge.