JPH1115185A - Electrophotographic photoreceptor, process cartridge having the photoreceptor and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a uniform surface layer free from light scattering and bleeding and low in surface every and enhanced in both of mechanical and electric durabilities by incorporating a resin obtained by polycondensing a specified organosilicon-modified positive hole transfer compound as a monomer component in a surface layer. SOLUTION: The surface layer contains as a monomer component the resin obtained by polycondensing the organosilicon-modified positive hole-transferring compound represented by the formula in which A is a positive hole transferring group; Q is a hydrolyzale or hydroxyl group; R<2> is a univalent optionally substituted hydrocarbon group; R<3> is an optionally substituted alkylene or arylene group; (m) is 1, 2, or 3; l is a positive integer; and mxl=>=3. Q is a hydrolyzable group, such as methoxy or ethoxy group, and further preferably, an -OR<1> group, and R<1> is a group for forming a hydrolyzable alkoxy group or the like and its carbon number is, preferably, 1-6, and Q is, preferably, an alkoxy group -OR<1> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member having a specific surface layer, a process cartridge having the electrophotographic photosensitive member, and an image forming apparatus.

[0002]

2. Description of the Related Art A charging means,
Since an electrical or mechanical external force is directly applied by the developing unit, the transferring unit, the cleaning unit, and the like, durability against them is required.

More specifically, the photoreceptor is required to have durability against abrasion and scratches on the surface of the photoreceptor due to rubbing and deterioration of the surface of the photoreceptor due to ozone which is likely to be generated during corona discharge under high humidity. In addition, there is a problem that toner adheres to the surface of the photoconductor due to repetition of development and cleaning. For this purpose, improvement in the cleaning property of the surface of the photoconductor is required.

Attempts have been made to provide various surface protective layers containing a resin as a main component on the photosensitive layer in order to satisfy the various characteristics required on the surface of the photosensitive member as described above. For example, JP-A-57-30843 proposes a protective layer in which resistance is controlled by adding metal oxide particles as conductive particles.

It has also been studied to improve the physical properties of the photoreceptor surface by adding various substances to the surface layer. For example, as an additive focused on low surface energy of silicone, silicone oil (JP-A-61-13)
2954), polydimethylsiloxane, silicone resin powder (JP-A-4-324454), cross-linked silicone resin, poly (carbonate silicone) block copolymer, silicone-modified polyurethane and silicone-modified polyester.

A typical polymer having a low surface energy is a fluorinated polymer.
Examples include polytetrafluoroethylene powder and carbon fluoride powder.

[0007]

However, although a surface protective layer containing a metal oxide or the like can have high hardness, it has a problem in cleaning properties and the like because the surface energy is easily increased. Silicone resins are excellent in that they have low surface energy, but do not show sufficient compatibility with other resins, so they tend to agglomerate in the additive system, causing light scattering or bleeding and segregating on the surface. There were problems such as not exhibiting stable characteristics. In addition, fluoropolymers, which are low surface energy polymers, are generally insoluble in solvents and poor in dispersibility, so it is difficult to obtain a smooth photoreceptor surface, and the refractive index is small. There is a problem that scattering is liable to occur, which causes deterioration of transparency. Further, there is a problem that the fluorine-based polymer is generally soft and easily damaged.

An object of the present invention is to solve the above-mentioned problems, that is, to provide a uniform surface layer without light scattering or bleed, and to achieve low surface energy and mechanical and electrical durability. An object of the present invention is to provide a compatible electrophotographic photosensitive member, and a process cartridge and an image forming apparatus having the electrophotographic photosensitive member.

[0009]

That is, the present invention provides an electrophotographic photosensitive member having a support and a photosensitive layer on the support, wherein the surface layer of the electrophotographic photosensitive member has the following formula (1):

[0010]

Embedded image (A represents a hole transporting group, Q represents a hydrolyzable group or a hydroxyl group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group, and R ³ represents a substituted or unsubstituted alkylene group or arylene. M represents an integer of 1 to 3;
Represents a positive integer, and m × l is 3 or more. An electrophotographic photoreceptor comprising a resin obtained by polycondensing the organosilicon-modified hole-transporting compound represented by the formula (1) as a monomer component.

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

In the present invention, the resin is represented by the above formula (1)
Is preferably obtained by polycondensing only the organosilicon-modified hole-transporting compound represented by the following formula as a monomer component. This is because all monomers of the resin have a hole transporting group, so that an electrophotographic photosensitive member having a very low residual potential can be obtained.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (1), Q represents a hydrolyzable group or a hydroxyl group.
Methoxy group, an ethoxy group, a methyl ethyl ketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group and a methoxyethyl group, more preferably represented by -OR ^1. R ¹
Is a group that forms an alkoxy group or an alkoxyalkoxy group that is a hydrolyzable group, and preferably has 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. And a methoxyethyl group. As Q, an alkoxy group represented by the formula —OR ¹ is preferable. In general, when the number m of the hydrolyzable groups bonded to the silicon atom is 1 or 2, condensation by the organosilicon compound itself hardly occurs and the polymerization reaction is suppressed, but when m is 3, the condensation reaction is performed. Since the crosslinking reaction can easily occur and the crosslinking reaction can be performed to a high degree, improvement in the hardness and the like of the obtained cured product can be expected.

Therefore, in the present invention, m is preferably 3.

R ² is a monovalent hydrocarbon group directly bonded to a silicon atom and preferably has 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. Can be Other examples include alkenyl groups such as vinyl group and allyl group, and aryl groups such as phenyl group and tolyl group. Examples of the substituent that R ² may have include a halogen atom such as fluorine.
Examples of the halogen-substituted monovalent hydrocarbon group include a fluorohydrocarbon group represented by a trifluoropropyl group, a heptafluoropentyl group, a nonafluorohexyl group, and the like.

R ³ represents an alkylene group or an arylene group and preferably has 1 to 18 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a cyclohexylidene group, a phenylene group, a biphenylene group, a naphthylene group And a group to which these are bonded. Examples of the substituent which R ³ may have include an alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, and a halogen atom such as a fluorine atom and a chlorine atom.

In these, R ³ is represented by the formula — (CH ₂ ) _n −
(N is a positive integer). n is 1 to
More preferably, it is not necessary to be 18. When n is 19 or more, the hole transporting group A easily moves, so that the hardness is lowered. When the hole transporting group is directly bonded to the silicon atom, stability and physical properties are easily adversely affected due to steric hindrance or the like. n is more preferably 2 to 8.

Further, m represents an integer of 1 to 3, 1 represents a positive integer, and m × l is 3 or more. Further, l is 1 to
It is preferably 5. When 1 is 6 or more, unreacted groups tend to remain in the polycondensation reaction, so that electrophotographic properties and the like are apt to be reduced.

The hole transporting property in the present invention refers to the ability to transport holes, and preferably has an ionization potential of 6.2 eV or less. That is, the hydrogenated product of the modified organosilicon hole transporting compound represented by the above formula (1) and A has an ionization potential of 6.2 eV.
Or less, particularly 4.5 to 6.2 eV.
It is preferred that The ionization potential is 6.2
If it exceeds eV, hole injection is unlikely to occur and charging becomes easy. If it is less than 4.5 eV, the compound is easily oxidized and thus easily deteriorates. The ionization potential is measured by a photoelectron analyzer (manufactured by Riken Keiki Co., surface analyzer AC-
It is measured by 1).

It is preferable that the modified organosilicon hole transporting compound has a hole mobility of 1 × 10 ⁻⁷ cm ² / Vsec or more. 1x1
If it is less than 0 ^-7 cm ² / Vsec, holes may not move sufficiently before development after exposure as an electrophotographic photoreceptor, which may cause a problem that apparently sensitivity is reduced and residual potential is increased. .

As the hole transporting group A in the above formula (1),
Any material may be used as long as it exhibits hole transportability.
As the hydrogenation compound (hole transporting compound), for example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (p-diethylaminostyryl) anthracene, 1,1 -Bis- (4-dibenzylaminophenyl) propane, styrylanthracene,
Examples include styrylpyrazolin, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, and N-phenylcarbazole derivatives.

As the hole transporting group A, those having a structure represented by the following formula (2) are preferable.

[0023]

Embedded image (R ⁴ , R ⁵ and R ⁶ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ⁴ , R ⁵ and R ⁶ are the same or different. Thus, the hole transporting group A is a group formed by removing the hydrogen atom of one of R ⁴ , R ⁵ and R ⁶ .

Preferred specific examples of the structure of R ⁴ , R ⁵ and R ⁶ are shown below.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

As a method for synthesizing the organosilicon-modified hole-transporting compound of the above formula (1), there are known methods, for example, a method in which a compound having a vinyl group on an aromatic ring and a silicon hydride compound having a substituent are converted into platinum. A catalyst which performs a hydrosilylation reaction using a system catalyst or an organic peroxide as a catalyst is suitably used. The platinum catalyst used in this case is not particularly limited, and may be any platinum catalyst used in ordinary hydrosilylation reactions and addition-type silicone rubbers, such as platinum chloride, chloroplatinic acid, and a platinum-olefin complex. And a platinum-phosphine complex. The amount of the platinum catalyst to be added is not particularly limited, but it is preferable to use the platinum catalyst in the smallest possible amount so that the residual catalyst does not adversely affect the properties. When the compound of the present invention is synthesized by an addition reaction from a compound having a vinyl group on an aromatic ring and a silicon hydride compound having a substituent with a platinum-based catalyst or the like, when the compound reacts with the α-position of the vinyl group, And may form a mixture. In the present invention, those reacted at either the α-position or the β-position may be used. However, when the number of carbon atoms in the hydrocarbon group bonding the silicon atom and the hole-transporting group is small, the β-position may be sterically hindered. Are preferred.

As the organic peroxide, any organic peroxide having a half-life at room temperature or higher can be used. In particular, an alkyl peroxide such as lauryl peroxide can be suitably used because hydrogen extraction hardly occurs. Those having no vinyl group can be used as a raw material for synthesis of the present invention by, for example, a method of formylating an aromatic ring, reducing and dehydrating or directly introducing a vinyl group by Wittig reaction.

A catalyst is not always required for the hydrolysis and polycondensation of the modified organosilicon hole transporting compound, but it does not hinder the use of a catalyst usually used for hydrolysis and polycondensation of a silicon resin. In consideration of the time required for hydrolysis and polycondensation, the curing temperature, etc., it is appropriately selected from alkyltin organic acid salts such as dibutyltin diacetate, dibutyltin dilaurate and dibutyltin octoate or organic titanates such as normal butyl titanate. You.

In the present invention, a three-dimensional crosslinked structure is formed at the time of polycondensation of the modified organosilicon hole transporting compound, which makes it difficult to move between the elements and to invade the compound from the outside. The hardness and the mechanical strength are increased, and not only the wear resistance is improved, but also the durability against electric obstacles such as arc discharge generated at the time of charging and chemical substances is improved.

In the present invention, the coating may be formed and then cured, or the coating may be formed and cured after partially polycondensing the hole transporting compound in advance. When the hole transporting compound is partially polycondensed in advance, any solution or dispersion that does not hinder application to the photoreceptor can be used.

As a curing condition, it is preferable to heat at 100 to 200 ° C. If the temperature is lower than 100 ° C., the curing reaction takes a long time, so that an unreacted hydrolyzable group may remain. When the temperature exceeds 200 ° C., the hole transporting group is liable to be oxidized and deteriorated, and adverse effects are apt to occur. More preferably, 1
It is used after being cured by heating at 20 to 160 ° C.

An example of producing an electrophotographic photosensitive member using the curable compound having a hole transporting ability of the present invention will be described below.

As the support (1 in FIGS. 1 and 2) of the electrophotographic photosensitive member, the support itself has conductivity, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, chromium, titanium, nickel, Magnesium, indium, gold, platinum, silver, iron and the like can be used. In addition, a material in which aluminum, indium oxide, tin oxide, gold, or the like is formed on a derivative support such as a plastic by vapor deposition or the like, a material in which conductive fine particles are mixed with plastic or paper, or the like can be used. It is important that these conductive supports have uniform conductivity and have a smooth surface. Since the surface smoothness greatly affects the uniformity of the undercoat layer, the charge generation layer and the hole transport layer formed thereon, the surface roughness is set to 0.1.
It is preferably used at 3 μm or less. Irregularities exceeding 0.3 μm greatly change the local electric field applied to a thin layer such as an undercoat layer or a charge generation layer, so that its characteristics are greatly changed, and defects such as charge injection and uneven residual potential are caused. This is not preferable because it is liable to occur.

In particular, the conductive layer (2 in FIGS. 1 and 2) obtained by dispersing and applying conductive fine particles in a polymer binder is easy to form and is suitable for forming a uniform surface. . The primary particle size of the conductive fine particles used at this time is 100 nm or less, and more preferably 5 nm or less.
Those having a thickness of 0 nm or less are used. As the conductive fine particles, conductive zinc oxide, conductive titanium oxide, Al, Au,
Cu, Ag, Co, Ni, Fe, carbon black, I
TO, tin oxide, indium oxide, indium and the like are used, and these may be used by coating the surface of the insulating fine particles. The content of the conductive fine particles is used so that the volume resistance is sufficiently low.
It is added so as to have a resistance of ¹⁰ Ωcm or less. More preferably, it is used at 1 × 10 ⁸ Ωcm or less.

When exposure is performed using a coherent light source such as a laser, it is also possible to form irregularities on the surface of the conductive support in order to prevent image deterioration due to interference. In this case, irregularities such as about 1 / 2λ of the wavelength used are dispersed with an insulator such as silica beads having a diameter of several μm or less so that defects such as charge injection and unevenness of the residual potential do not easily occur. It can be formed and used.

In the present invention, an undercoat layer having an injection inhibiting function and an adhesive function is provided between the support and the photosensitive layer (FIGS. 1 and 2).
3) can be provided. Casein, polyvinyl alcohol, nitrocellulose,
Examples include ethylene-acrylic acid copolymer, polyvinyl butyral, phenolic resin, polyamide, polyurethane and gelatin. The thickness of the undercoat layer is 0.1 to 10 μm
m, more preferably 0.3 to 3 μm.

The photosensitive layer comprises a charge generating layer containing a charge generating substance (4 in FIGS. 1 and 2) and a charge transporting layer containing a hole transporting compound (5 in FIGS. 1 and 2). A single-layer type (not shown) containing a charge-generating substance and a hole-transporting compound in the same layer is used.

As the charge generating material, for example, selenium
Tellurium, pyrylium dye, thiopyrylium dye, phthalocyanine pigment, anthantrone pigment, dibenzopyrenequinone pigment, pyranthrone pigment, trisazo pigment, disazo pigment, azo pigment, indigo pigment, quinacridone pigment and Cyanine pigments and the like can be used.

The resin obtained by polycondensing the hole transporting compound of the present invention can be used as a charge transporting layer (5 in FIG. 1) or a surface protective layer having a hole transporting ability (6 in FIG. 2). is there.

When used as a single-layer photoreceptor, good characteristics can be obtained by using the charge generating substance in combination with the hole transporting compound of the present invention.

The hole transporting compound of the present invention can be used in combination with other hole transporting compounds. Examples of such hole transporting compounds include poly-N-vinylcarbazole and polystyrylanthracene. Polymer compounds having a heterocyclic or condensed polycyclic aromatic compound, such as pyrazoline, imidazole, oxazole, oxadiazole, heterocyclic compounds such as triazole and carbazole, triarylalkane derivatives such as triphenylmethane, and triphenylamine. Low molecular compounds such as a triarylamine derivative, a phenylenediamine derivative, an N-phenylcarbazole derivative, a stilbene derivative, and a hydrazone derivative can be used.

As the charge generating substance and the hole transporting compound, a binder polymer is used if necessary. Examples of binder polymers include styrene, vinyl acetate, vinyl chloride, acrylates, methacrylates,
Polymers and copolymers of vinyl compounds such as vinylidene fluoride and trifluoroethylene, polyvinyl alcohol,
Examples include polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

In addition to the above compounds, additives can be used in the photosensitive layer and the protective layer in order to improve mechanical properties and durability. As such additives, an antioxidant, an ultraviolet absorber, a stabilizer, a crosslinking agent, a lubricant, a conductivity control agent, and the like are used.

The thickness of the charge generation layer in the present invention is 3 μm
It is preferable that it is below, and it is especially preferable that it is 0.01-1 micrometer. The charge transport layer has a thickness of 1 to 4.
It is preferably 0 μm, and particularly preferably 3 to 30 μm.

When the photosensitive layer is of a single-layer type, its thickness is preferably from 1 to 40 μm, particularly preferably from 3 to 3 μm.
It is preferably 0 μm.

The thickness of the surface protective layer in the present invention is from 1 to
It is preferably 15 μm. If it is less than 1 μm, the protective effect is not sufficient, and if it exceeds 15 μm, the film thickness of the entire photosensitive layer increases, which is not preferable since image deterioration is likely to occur.

In the present invention, the product of the spot area of the light beam irradiated by the exposure means and the thickness of the photosensitive layer of the electrophotographic photosensitive member is preferably 2 × 10 ⁴ μm ³ or less. This product is 2 × 10 ³ μm ^{3 in} terms of the magnitude of the development contrast (the potential difference on the photoconductor during development).
It is preferable that it is above. If it is less than 2 × 10 ³ μm ³ , it tends to be difficult to obtain a sufficient development contrast.

In this case, the exposure method used in the present invention forms an electrostatic latent image on a photoreceptor by irradiating light in the form of dots. The light source is not particularly limited, but is preferably laser light and LED light in that a smaller spot area can be more easily obtained.

FIG. 3 shows the relationship between the light intensity distribution, the spot diameter and the product of the spot area (S) and the thickness of the photosensitive layer. The light spot generally has an elliptical shape having a main scanning spot diameter (ab) and a sub-scanning spot diameter (cd) as shown in FIG. The product of the heights can be said to be the volume (V) of the portion where the light spot is irradiated on the photosensitive layer.

The light spot area (S) is the area on the photosensitive layer, and the light intensity is 1 / e of the peak intensity (A).
² (B) It is represented by the area of the portion that is equal to or greater than (B). Examples of the light source used include a semiconductor laser and an LED. The light intensity distribution includes a Gaussian distribution and a Lorentz distribution. In each case, 1 / e of the peak intensity (A) is used.
² A portion having an intensity higher than (B) is defined as a spot area (S). In addition, the spot area (S) is the position of the photoconductor at CC.
It can be measured by installing a D camera.

In the present invention, the light spot area is 4 × 1.
0 ³ μm ² or less, especially 3 × 10
It is preferably ³ μm ² or less. 4 × 10 ³ μm ²
When the value exceeds, light of an adjacent pixel easily overlaps, and the tone reproducibility tends to be unstable. In addition, 1 × 10 ³
It is preferably at least ² μm ² .

From the above viewpoint, the thickness of the photosensitive layer in the present invention is preferably 12 μm or less, more preferably 10 μm or less.
It is preferably not more than μm.

The electrophotographic photoreceptor of the present invention has extremely excellent mechanical strength and surface lubricity, and is therefore very preferable as a photoreceptor used in such a system.

FIG. 4 shows a schematic configuration of a first example of an image forming apparatus having the process cartridge of the present invention.

In FIG. 7, reference numeral 7 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 8 at a predetermined peripheral speed in a direction indicated by an arrow. In the rotation process, the photosensitive member 7 is uniformly charged on its peripheral surface with a predetermined positive or negative potential by the primary charging means 9, and then the image exposure 10 from an image exposure means (not shown) such as laser beam scanning exposure. Receive. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 7.

The formed electrostatic latent image is developed with toner by the developing means 11, and the developed toner developed image is rotated between the photosensitive member 7 and the transfer means 12 from a paper feeding unit (not shown). The recording medium 13 is sequentially transferred to the transfer material 13 taken out and fed in synchronism with the above.

The transfer material 13 having undergone the image transfer is separated from the surface of the photoreceptor, introduced into the image fixing means 14 and subjected to image fixing to be printed out as a copy (copy) outside the apparatus.

The surface of the photoreceptor 7 after the image transfer is cleaned and cleaned by removing the untransferred toner by the cleaning means 15, and the pre-exposure light 1 from the pre-exposure means (not shown).
After being subjected to the static elimination processing by 6, it is repeatedly used for image formation. When the primary charging unit 9 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 7, primary charging means 9, developing means 11 and cleaning means 15 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from an image forming apparatus main body such as a copying machine or a laser beam printer. For example, the process cartridge 17 may be integrally supported with the primary charging means 9 and formed into a cartridge, and the process cartridge 17 may be attached to and detached from the apparatus main body by using guide means such as rails 18 of the apparatus main body.

FIG. 5 shows a schematic configuration of a color copying machine which is a second example of the image forming apparatus of the present invention.

In the figure, reference numeral 201 denotes an image scanner, which reads a document and performs digital signal processing. Reference numeral 202 denotes a printer unit which prints out an image corresponding to the document image read by the image scanner 201 on a sheet in full color.

In the image scanner unit 201, 20
Reference numeral 0 denotes an original plate, and the original 20 on the original platen glass 203
4 is used for fixing. The document 204 is irradiated with light from a halogen lamp 205 passing through an infrared cut filter 208. The reflected light from the document 204 is reflected on the mirror 20.
6, 207, and three CCDs by lens 209
3-line sensor (hereinafter referred to as CCD)
) Is formed on the image 210. The CCD 210 separates the light information from the document into colors and sends it to the signal processing unit 211 as red (R), green (G), and blue (B) components of the full color information. Note that 205 and 206 are speeds v and 207 is １ ／ v by mechanically moving in a direction perpendicular to the electrical scanning direction (hereinafter, main scanning direction) of the line sensor (hereinafter, sub-scanning direction). Scans the entire original.

The signal processor 211 electrically processes the read signal, decomposes the signals into magenta (M), cyan (C), yellow (Y), and black (BK) components, and sends them to the printer unit 200. Thus, one printout is completed by scanning the document four times in total.

The M, C, Y and BK image signals sent from the image scanner unit 201 are sent to the laser driver 212. The laser driver 212 modulates and drives the semiconductor laser 213 according to the image signal. The laser beam scans on the photosensitive drum 217 via the polygon mirror 214, the f-θ lens 215, and the mirror 216.

Reference numeral 218 denotes a rotary developing device, which includes a magenta developing device 219, a cyan developing device 220, and a yellow developing device 221.
And a black developing device 222. The four developing devices alternately contact the photosensitive drum, and develop the electrostatic latent images of M, C, Y, and BK formed on the photosensitive drum 217 with the corresponding toner. .

Reference numeral 223 denotes a transfer drum.
4 or 225 to the transfer drum 2
23, and the toner image developed on the photosensitive drum 217 is transferred to a sheet.

After the four colors M, C, Y and BK are sequentially transferred in this manner, the sheet passes through the fixing unit 226 and is discharged after being fixed.

[Synthesis Example 1] Synthesis of 4- [2- (triethoxysilyl) ethyl] triphenylamine <Synthesis of 4- (N, N-diphenylamino) benzaldehyde>
4 g and 35.5 ml of DMF were added, and 84.4 ml of phosphorus oxychloride was added dropwise with stirring under ice-water cooling.
The mixture was heated to 5 ° C. and reacted for 5 hours. The reaction solution was poured into 4 liters of warm water and stirred for 1 hour. Then, the precipitate is collected by filtration,
After washing with a mixed solution of ethanol / water (1: 1),
(N, N-diphenylamino) benzaldehyde was obtained. Yield 91.5 g (81.0% yield).

<Synthesis of 4-vinyltriphenylamine>
14.6 g of sodium hydride and 700 ml of 1,2-dimethoxyethane were placed in a three-necked flask, and stirred at room temperature while adding 130.8 g of trimethylphosphonium bromide.
g was added. Next, after adding a drop of absolute ethanol, 7
The reaction was performed at 0 ° C. for 4 hours. To this was added 100 g of 4- (N, N-diphenylamino) benzaldehyde,
And the reaction was carried out for 5 hours. The reaction solution was filtered, and the filtrate and the ether extract of the precipitate were combined and washed with water. Next, the ether solution was dehydrated with calcium chloride, and the ether was removed to obtain a reaction mixture. This was recrystallized from ethanol to obtain acicular, pale yellow vinyltriphenylamine. Yield 83.4 g (84.0% yield).

<Hydrosilylation of 4-vinyltriphenylamine> Toluene 40 ml, triethoxysilane 9.
9 g (60 mmol) and 0.01 solution of tris (tetramethyldivinyldisiloxane) diplatinum (0) in toluene
8 mmol was placed in a three-necked flask, and 20 ml of a toluene solution of 8.2 g of 4-vinyltriphenylamine was added dropwise with stirring at room temperature. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure.
[2- (Triethoxysilyl) ethyl] triphenylamine was obtained. Yield 12.1 g (91.7% yield).

The H-NMR spectrum is shown in FIG. 6 (APC300 NMR spectrometer manufactured by Bruker).
The ionization potential of this compound was 5.68 eV as measured by a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1).

This compound was applied on a copper substrate by a wire bar coating method, and thermally cured at 120 ° C. for 12 hours to form a film of about 8 μm. Next, a translucent gold electrode was formed by vapor deposition.

The pulse width of this sample is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
When the drift mobility was measured by the f-flight method, it was 1 × 10 ⁻⁷ cm ² / Vsec.

[Synthesis Example 2] 4,4'-bis [2- (triethoxysilyl) ethyl]
Synthesis of triphenylamine <Synthesis of N, N-bis (4-formylphenyl) aminobenzene> Triphenylamine was placed in a three-necked flask.
7 g and 35.5 ml of DMF were added, and 84.4 ml of phosphorus oxychloride was added dropwise with stirring under ice-water cooling. After completion of the dropwise addition, the mixed solution was reacted at 95 ° C. for 5 hours, poured into 5 L of warm water, and stirred for 1 hour. Thereafter, the precipitate was collected by filtration, washed with a mixed solution of ethanol / water (1: 1),
N, N-bis (4-formylphenyl) aminobenzene was obtained. 65.3 g (95.9% yield).

<Synthesis of N, N-bis (4-vinylphenyl) aminobenzene> 4.8 g of sodium hydride and 700 ml of 1,2-dimethoxyethane were placed in a three-necked flask, and methyltriphospho was stirred at room temperature. 73.2 g of nickel bromide were added. Next, after a drop of absolute ethanol was added, the mixture was reacted at 70 ° C. for 4 hours. 30.0 g of N, N-bis (4-formylphenyl) aminobenzene was added to the reaction mixture thus obtained,
After reacting at 5 ° C. for 5 hours, the mixture was washed with water and extracted with toluene.
Next, the toluene solution was dehydrated with calcium chloride, and the solvent was removed to obtain pale yellow N, N-bis (4-vinylphenyl) aminobenzene. Yield 18.4 g (yield 6
2.2%).

<Hydrosilylation of N, N-bis (4-vinylphenyl) aminobenzene> A toluene solution of 40 ml of toluene, 9.9 g (60 mmol) of triethoxysilane and diplatinum (0) of tris (tetramethyldivinyldisiloxane) 0.018 mmol was placed in a three-necked flask, and 20 ml of a toluene solution of 2.6 g (8.7 mmol) of N, N-bis (4-vinylphenyl) aminobenzene was added dropwise with stirring at room temperature. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and the solvent was removed under reduced pressure to obtain pale yellow oily 4,4′-bis [2- (triethoxysilyl) ethyl] triphenylamine. Yield 4.4 g (80.6% yield).

The ionization potential of this compound was measured using a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., surface analyzer AC-1).
Was 5.67 eV.

This compound was applied on a copper substrate by a wire bar coating method and thermally cured at 120 ° C. for 12 hours to form a film of about 5 μm. Next, a translucent gold electrode was formed by vapor deposition.

For this sample, the pulse width is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
The drift mobility measured by the f-flight method was 3 × 10 ⁻⁷ cm ² / Vsec.

[Synthesis Example 3] Synthesis of 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- (triethoxysilyl) ethyl] benzene <N, N-bis (3,4 Synthesis of -dimethylphenyl) aminobenzene> 38.5 g of 4-iodo-o-xylene
(166 mmol), 22.9 g of anhydrous potassium carbonate (1
66 mmol) and 7.0 g of copper powder in nitrobenzene 20
Then, the mixture was heated under reflux with stirring for 8 hours. After cooling, the precipitate was removed by filtration. The obtained reaction mixture was passed through a silica gel column to obtain N, N-bis (3,4-dimethylphenyl) aminobenzene. Yield 15.7 g (yield 69
%).

<Synthesis of 4- [N, N-bis (3,4-dimethylphenyl) amino] benzaldehyde> [N, N-bis (3,4-dimethylphenyl)
Amino] benzene 124.6 g and DMF 35.5 ml
And add phosphorus oxychloride 8 with stirring under ice-water cooling.
4.4 ml were added dropwise. After completion of dropping, the mixed solution is heated to 95 ° C.
For 5 hours and poured into 4 liters of warm water and stirred for 1 hour. Thereafter, the precipitate was collected by filtration, and ethanol / water (1:
After washing with the mixed solution of 1), 4- [N, N-bis (3,4
-Dimethylphenyl) amino] benzaldehyde was obtained. Yield 107.6 g (79.0% yield).

<Synthesis of 4- [N, N-bis (3,4-dimethylphenyl) amino] styrene> 12.1 g of sodium hydride and 580 ml of 1,2-dimethoxyethane were placed in a three-necked flask and allowed to stand at room temperature. While stirring, 108.5 g of trimethylphosphonium bromide was added. Next, after a drop of absolute ethanol was added, the mixture was reacted at 70 ° C. for 4 hours. The reaction mixture obtained as described above was added to 4-
[N, N-bis (3,4-dimethylphenyl) amino]
After adding 100.0 g of benzaldehyde and reacting at 70 ° C. for 5 hours, the mixture was separated by filtration, and the cake collected by filtration was extracted with ether, combined with the filtrate, and washed with water. Next, the ether solution was dehydrated with calcium chloride, and the ether was removed to obtain a reaction mixture. This was recrystallized twice with ethanol to give a needle-shaped, 4-
[N, N-bis (3,4-dimethylphenyl) amino]
Styrene was obtained. The yield was 84.5 g (85.0% yield).

<Hydrosilylation of 4- [N, N-bis (3,4-dimethylphenyl) amino] styrene> 40 ml of toluene, 6.0 g of triethoxysilane and tris (tetramethyldivinyldisiloxane) diplatinum (0) 0.54 mmol of toluene solution was placed in a three-necked flask, and 4- [N, N-bis (3,4-
20 ml of a toluene solution of 9.9 g of dimethylphenyl) amino] styrene was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure, and 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- ( [Triethoxysilyl) ethyl] benzene was obtained. Yield 13.4 g (90.1% yield).

The H-NMR spectrum is shown in FIG. 7 (APC300 NMR spectrometer manufactured by Bruker).
The C-NMR spectrum is shown in FIG.
PC300 NMR spectrometer).

The ionization potential of this compound was measured using a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., surface analyzer AC-1).
Was 5.26 eV.

This compound was applied on a copper substrate by a wire bar coating method, and thermally cured at 120 ° C. for 12 hours to form a film of about 5 μm. Next, a translucent gold electrode was formed by vapor deposition.

The pulse width of this sample is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
When the drift mobility was measured by the f-light method, it was 9 × 10 ⁻⁷ cm ² / Vsec.

Synthesis Example 4 Synthesis of 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- (triethoxysilyl) ethyl] benzene <4- [N, N-bis ( 3,4-Dimethylphenyl) amino] styrene hydrosilylation> toluene 40 ml,
6.0 g (37 mmol) of triethoxysilane and dichloro (h-cycloocta-1,5-diene) platinum (II)
0.34 mmol was placed in a three-necked flask and stirred at room temperature while stirring 20 ml of a toluene solution of 9.9 g of 4- [N, N-bis (3,4-dimethylphenyl) amino] styrene.
Was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure to give 4- [N, N
-Bis (3,4-dimethylphenyl) amino]-[2-
(Triethoxysilyl) ethyl] benzene was obtained. Yield 14.0 g (94.2% yield).

The ionization potential of this compound was measured using a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1).
Was 5.31 eV.

This compound was applied on a copper substrate by a wire bar coating method, and thermally cured at 120 ° C. for 12 hours to form a film of about 5 μm. Next, a translucent gold electrode was formed by vapor deposition.

The pulse width of this sample is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
When the drift mobility was measured by the f-light method, it was 7 × 10 ⁻⁷ cm ² / Vsec.

Synthesis Example 5 Synthesis of 4- [3- (triethoxysilyl) propyl] triphenylamine <Synthesis of 4-bromotriphenylamine> 8.0 g (45 mmol) of N-bromosuccinimide and triphenylamine 10 2.0 g (41 mmol) was placed in a 200 ml three-necked flask, and N, N-dimethylformamide 15 was added.
After adding 0 ml, the mixture was stirred overnight at room temperature. Then
The N, N-dimethylformamide was removed and the resulting solid was extracted with carbon tetrachloride. Thereafter, carbon tetrachloride was removed, and the obtained reaction mixture was recrystallized twice with ethanol to obtain 4-bromotriphenylamine as a white solid.
The yield was 8.2 g (61.7% yield).

<Synthesis of 4-N, N-diphenylaminoallylbenzene> 1.0 g (40 mmol) of magnesium metal was placed in a 300 ml four-necked flask, and the atmosphere was replaced with nitrogen. Next, 100 ml of diethyl ether was added and stirring was started. There 4-bromotriphenylamine 8.6
g (27 mmol) dissolved in diethyl ether 3
0 ml was slowly added dropwise. Approximately 3 ml was added dropwise, and reflux started slowly. While refluxing, the dropwise addition of the diethyl ether solution was further continued, and after the completion of the dropwise addition, reflux was further performed for 1 hour. The Grignard reagent solution obtained as described above is returned to room temperature, and then allyl chloride
40 ml of 1 g (27 mmol) of diethyl ether solution
Was slowly added dropwise while cooling with ice. After the dropwise addition, the reaction mixture was refluxed for 2 hours to mature the reaction. After that, 50m of water
1 was added while cooling with ice to effect hydrolysis. Next, the ether layer was extracted, washed once with a saturated aqueous solution of sodium hydrogen carbonate and twice with water, and then dried over anhydrous sodium sulfate.
After drying, the diethyl ether was removed and 4-N,
N-diphenylaminoallylbenzene was obtained. Yield 4.
9 g (63.2% yield).

<Hydrosilylation of 4-N, N-diphenylaminoallylbenzene> 40 ml of toluene, 6.0 g (37 mmol) of triethoxysilane and 0.54 mmol of a toluene solution of tris (tetramethyldivinyldisiloxane) diplatinum (0) In a three-necked flask, and stirring at room temperature, a solution of 9.7 g (34 mmol) of 4-N, N-diphenylaminoallylbenzene in toluene (20 m) was prepared.
1 was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure.
(Triethoxysilyl) propyl] triphenylamine was obtained. Yield 10.7 g (70.1% yield).

The ionization potential of this compound was measured using a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1).
Was 5.72 eV.

This compound was applied on a copper substrate by a wire bar coating method and thermally cured at 120 ° C. for 12 hours to form a film having a thickness of about 9 μm. Next, a translucent gold electrode was formed by vapor deposition.

The pulse width of this sample is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
When the drift mobility was measured by the f-flight method, it was 1.4 × 10 ⁻⁷ cm ² / Vsec.

Synthesis Example 6 Synthesis of 4- [4- (triethoxysilyl) butyl] triphenylamine <Synthesis of 4-methyltriphenylamine> 4.5 g (27 mmol) of diphenylamine, p-iodotoluene 1
1.0 g (51 mmol), 5.5 g of anhydrous potassium carbonate
(40 mmol) and 1.1 g of copper powder were added to 30 ml of o-dichlorobenzene, and the mixture was heated under reflux with stirring for 7 hours.
After completion of the reaction, the reaction solution was filtered, and the filtrate was washed successively with a 3 to 5% aqueous solution of sodium thiosulfate and saturated saline, and the organic layer was dried over anhydrous sodium sulfate and the solvent was removed. The obtained reaction mixture was recrystallized using ethanol to obtain 4
-Methyltriphenylamine was obtained. Yield: 5.7 g (81.4% yield).

<Synthesis of 4-bromomethyltriphenylamine> N-bromosuccinimide (6.9 g, 39 mmol)
l) and 9.1 g of 4-methyltriphenylamine (35
mmol) was placed in a 300 ml three-necked flask, 100 ml of carbon tetrachloride was added, and the mixture was heated under reflux with stirring overnight. After the completion of the reaction, the reaction solution was cooled. Next, the reaction solution was filtered, the solvent was removed, and the obtained reaction mixture was recrystallized using ethanol to obtain 4-bromomethyltriphenylamine. Yield 10.8 g (Yield 91.2)
%).

<Synthesis of 4-N, N-diphenylaminophenyl-1-butene> 1.0 g (40 mmol) of magnesium metal was placed in a 200 ml four-necked flask, and the atmosphere was replaced with nitrogen. Next, 100 ml of diethyl ether was added and stirring was started. Thereto was slowly added dropwise 20 ml of a diethyl ether solution in which 9.1 g (27 mmol) of 4-bromomethyltriphenylamine was dissolved. Approximately 5 ml was added dropwise, and the reflux started slowly. While refluxing, the dropwise addition of the diethyl ether solution was further continued, and after the completion of the dropwise addition, reflux was further performed for 1 hour. The Grignard reagent solution thus obtained was returned to room temperature, and then a solution of 2.1 g (27 mmol) of allyl chloride in 20 ml of diethyl ether was slowly added dropwise while cooling with ice. After the dropwise addition, the reaction mixture was refluxed for 2 hours to mature the reaction. Thereafter, 50 ml of water was added while cooling with ice to effect hydrolysis.
Next, the ether layer was extracted, washed once with a saturated aqueous solution of sodium hydrogen carbonate and twice with water, and then dried over anhydrous sodium sulfate. After drying, diethyl ether was removed to obtain 4-N, N-diphenylaminophenyl-1-butene as a white solid. 5.5 g (66.7% yield).

<Hydrosilylation of 4-N, N-diphenylaminophenyl-1-butene> A toluene solution of 40 ml of toluene, 9.9 g (60 mmol) of triethoxysilane and diplatinum (0) of tris (tetramethyldivinyldisiloxane) 0.018 mmol is placed in a three-necked flask, and 16.7 g (54.7 mmol) of 4-N, N-diphenylaminophenyl-1-butene is stirred at room temperature.
Of toluene solution was added dropwise. After dropping, 70
After stirring at 3 ° C. for 3 hours, the solvent was removed under reduced pressure, and 4- [4- (triethoxysilyl) butyl] as a pale yellow oil was obtained.
Triphenylamine was obtained. Yield 13.9 g (yield 8
3.2%).

The ionization potential of this compound was measured using a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1).
Was 5.69 eV.

This compound was applied on a copper substrate by a wire bar coating method, and thermally cured at 120 ° C. for 12 hours to form a film of about 5 μm. Next, a translucent gold electrode was formed by vapor deposition.

The pulse width of this sample is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
When the drift mobility was measured by the f-flight method, it was 2 × 10 ⁻⁷ cm ² / Vsec.

[Synthesis Example 7] 10 g of 4- [2- (triethoxysilyl) ethyl] triphenylamine (Synthesis Example 1) was dissolved in 16.7 g of toluene, and 0.2 g of dibutyltin diacetate was added and mixed. This was applied to a glass plate using a bar coat, and 14
Dry at 0 ° C. for 15 hours. Observation with a microscope revealed that a uniform film was formed.

[Comparative Synthesis Example 1] 10 g of methyltriethoxysilane was dissolved in 16.7 g of toluene, and triphenylamine as a hole-transporting compound was dissolved at 30% by weight in methyltriethoxysilane, and dibutyltin diacetate was dissolved. 0.2 g was added and mixed. The mixture was mixed and cured in the same manner as in Synthesis Example 7 to form a film. The film became cloudy, and the precipitation of triphenylamine was observed under a microscope.

[Comparative Synthesis Example 2] A film was formed in the same manner as in Comparative Synthesis Example 1 except that phenyltriethoxysilane was used instead of methyltriethoxysilane. Although the opacity of the formed film was reduced, triphenylamine crystals were precipitated by microscopic observation.

[Comparative Synthesis Example 3] 4- [2- (trimethylsilyl) was reacted in the same manner as in Synthesis Example 1 except that 6 g (60 mmol) of trimethylsilane was used for hydrosilylation.
[Ethyl] triphenylamine was obtained. When this was used as a charge transporting compound to form a film in the same manner as in Comparative Synthesis Example 1, it was opaque and separation of 4- [2- (trimethylsilyl) ethyl] triphenylamine was observed.

[Comparative Synthesis Example 4] 10 g of methyltriethoxysilane was dissolved in 16.7 g of toluene, and the triarylamine compound used in Example 1 described later as a charge transporting compound was dissolved in 16.7 g of toluene with respect to methyltriethoxysilane. And dissolved and mixed and cured in the same manner as in Synthesis Example 7 to form a film. The film became cloudy, and precipitation of a triarylamine compound was observed under a microscope.

[Synthesis Example 8] Synthesis of 4- (N-ethyl-N-phenylamino)-[2- (triethoxysilyl) ethyl] benzene Synthesis of <4- (N-ethyl-N-phenylamino) benzaldehyde > 82 g of diphenylethylamine and 35.5 ml of DMF were added to a three-necked flask, and 84.4 ml of phosphorus oxychloride was added dropwise with stirring under cooling with ice water, and after completion of the addition, the temperature was raised to 95 ° C. and reacted for 5 hours. Was. Thereafter, the precipitate was collected by filtration and washed with a mixed solution of ethanol / water (1: 1) to obtain 4- (N-phenylamino) ethylbenzaldehyde. Yield 62 g.

<Synthesis of 4- (N-ethyl-N-phenylamino) styrene> 14.6 g of sodium hydride and 700 ml of 1,2-dimethoxyethane were placed in a three-necked flask, and trimethylphosphonate was stirred at room temperature. 130.8 g ofium bromide was added. Next, after adding one drop of absolute ethanol, the temperature was raised to 70 ° C., and the reaction was performed for 5 hours. The reaction solution was filtered, and the filtrate and the ether extract of the precipitate were combined and washed with water. Next, the ether solution was dehydrated with calcium chloride, and the ether was removed to obtain a reaction mixture. This was recrystallized from ethanol to obtain acicular, pale yellow crystals. Yield 62.4 g.

<Hydrosilylation of 4- (N-ethyl-N-phenylamino) styrene> A toluene solution of 40 ml of toluene, 9.9 g (60 mmol) of triethoxysilane and diplatinum (0) of tris (tetramethyldivinyldisiloxane) 0.018 mmol is placed in a three-necked flask, and stirred at room temperature while stirring a toluene solution of 7.6 g of 4-vinylphenyl (N-phenyl, N-ethyl) amine 20.
ml was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 3 hours, and then the solvent was removed under reduced pressure.
(N-ethyl-N-phenylamino)-[2- (triethoxysilyl) ethyl] benzene was obtained. Yield 7.8
g.

The ionization potential of this compound was measured using a photoelectron analyzer under atmospheric pressure (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1).
Was 6.3 eV.

This compound was applied on a copper substrate by a wire bar coating method and thermally cured at 120 ° C. for 12 hours to form a film of about 5 μm. Next, a translucent gold electrode was formed by vapor deposition.

The pulse width of this sample is 3 nsec.
Time-o using a 337 nm wavelength nitrogen laser
When the drift mobility was measured by the f-flight method, it was 2 × 10 ⁻⁸ cm ² / Vsec.

[0118]

【Example】

[Example 1] An alcohol-soluble copolymerized nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) was placed on an aluminum cylinder having an outer diameter of 80 mm created by mirror finishing.
A solution prepared by dissolving 5 parts (by weight, hereinafter the same) in 95 parts of methanol was applied by dip coating. 80
After drying at 10 ° C. for 10 minutes, an undercoat layer having a thickness of 1 μm was formed.

Next, as a dispersion for the charge generation layer, 5 parts of the following bisazo pigment was added to a solution prepared by dissolving 2 parts of polyvinyl benzal (a degree of benzalization of 75% or more) in 95 parts of cyclohexanone, and dispersed by a sand mill for 20 hours. . The thickness of the dispersion after drying was 0.2 μm on the undercoat layer formed earlier.
m by dip coating.

[0120]

Embedded image

Next, 5 parts of a triarylamine compound having the following structural formula and a polycarbonate resin (trade name)
Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 70 parts of chlorobenzene, and the solution for the charge transport layer was dissolved in 70 parts of chlorobenzene.
Then, 0.3 parts of silicone resin fine particles of m was added onto the above-mentioned charge generating layer by a dip coating method so that the film thickness after drying was 10 μm.

[0122]

Embedded image

Next, the 4- [N, N-
Bis (3,4-dimethylphenyl) amino]-[2-
(Triethoxysilyl) ethyl] benzene (100 parts) was dissolved in toluene (167 parts), and dibutyltin diacetate (2 parts) was added and mixed, and a solution was applied by spray coating.

By drying at 140 ° C. for 4 hours and heat curing, a 2 μm surface protective layer was formed.

When the electrophotographic photosensitive member was charged to -700 V and the electrophotographic characteristics were measured with light having a wavelength of 680 nm, E _1/2 (the amount of exposure necessary for decreasing the charging potential to -350 V) was 1 0.2 μJ / cm ² , residual potential −1
It was as good as 6V.

The electrophotographic photoreceptor was transferred to a Canon digital full-color copying machine CLC-500 at 63.5 in the sub-scanning direction.
μm, irradiation spot diameter of 20 μm in the main scanning direction (1 / e
² ) Initial charging using an evaluator modified to become -4
When the image was evaluated by setting to 00V, the initial and 1
After the endurance test of 100,000 sheets, there was no charge injection such as black spots, the abrasion amount of the photoreceptor was as small as 1.5 μm, an image output with excellent uniformity was obtained, and the gradation reproducibility was 256 gradations at 400 dpi. Very good.

[Comparative Example 1] An image of an electrophotographic photosensitive member produced in the same manner as in Example 1 except that the protective layer was not coated was evaluated. And no good image was obtained. The amount of wear of the photoreceptor was as large as 5 μm on 20,000 sheets.

Example 2 167 parts of a phenolic resin (trade name: Plyofen, manufactured by Dainippon Ink and Chemicals, Inc.) were dissolved in 100 parts of methyl cellosolve on an aluminum cylinder having an outer diameter of 30 mm obtained by drawing. A dispersion obtained by dispersing 200 parts of conductive barium sulfate ultrafine particles (primary particle diameter: 50 nm) and 3 parts of silicone resin particles having an average particle diameter of 2 μm by dip coating, and then drying to have a film thickness of 15 μm. A conductive layer was formed.

On the conductive layer, an alcohol-soluble copolymerized nylon (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.)
(5 parts) in 95 parts of methanol was applied by dip coating. After drying at 80 ° C. for 10 minutes, an undercoat layer having a thickness of 1 μm was formed.

Next, CuKα was used as the dispersion for the charge generation layer.
5 parts of an oxytitanium phthalocyanine pigment having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° in characteristic X-ray diffraction at Bragg angles (2θ ± 0.2 °) of 95 parts of cyclohexane Was added to a solution prepared by dissolving 2 parts of polyvinyl benzal (degree of benzalization of 75% or more), and dispersed by a sand mill for 2 hours.

This dispersion was applied by dip coating on the previously formed undercoat layer so that the film thickness after drying was 0.2 μm.

Then, 100 parts of the organosilicon-modified triarylamine compound synthesized in Synthesis Example 4 was added to toluene 167
The mixture was dissolved in 2 parts, and a solution obtained by adding 2 parts of dibutyltin diacetate and mixing was applied onto the charge generation layer by a dip coating method. After drying at 120 ° C. for 5 hours and heat curing, a transparent and uniform charge transport layer having a thickness of 10 μm was formed.

The pencil hardness is 5H and the contact angle of water is 10
5 degrees.

The electrophotographic photosensitive member was charged to -700 V, and the surface potential after one second without exposure was measured.
The dark decay was 40V.

When the electrophotographic characteristics were measured using light having a wavelength of 680 nm, E _1/2 (exposure required for decreasing the charging potential to −350 V) was 0.2 μJ / c.
m ^2, the residual potential was good and -22V.

This electrophotographic photoreceptor was used with a modified laser beam printer LBP-8IV (a spot diameter (1/1)).
e ² ) is 63.5 μm in the sub-scanning direction and 20 in the main scanning direction.
The image was evaluated by setting the initial charge to -500 V using a remodeling of μm, and the abrasion loss of the photoreceptor after the durability test of 4000 sheets was extremely small at 0.1 μm or less. Good at 100 degrees, no image degradation, 60
One-pixel reproducibility of a highlight portion in an input signal corresponding to 0 dpi was also sufficient.

Comparative Example 2 A charge transport layer in which 5 parts of the triarylamine compound used in Example 1 and 5 parts of a polycarbonate resin (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) were dissolved in 70 parts of chlorobenzene. A charge transport layer having a thickness of 10 μm after drying was formed by applying a liquid for use on the charge generation layer of Example 2 by a dip coating method. When the obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 2, after 4000 sheets of the durability test, interference fringes and black spots were recognized, the abrasion amount was as large as 1.8 μm, and the contact angle of water was 72 degrees. 600d
The reproducibility of one pixel of the highlight part in pi was also insufficient and there was unevenness.

Example 3 A phenol resin (trade name: Pryofen, manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in 167 parts of methylcellosolve in 100 parts of methylcellosolve on the same aluminum cylinder as in Example 2. A dispersion in which 200 parts of ultra-fine barium sulfate particles (primary particle diameter: 50 nm) were dispersed was applied by a dip coating method so that the film thickness after drying was 10 μm. The undercoat layer having a thickness of 1 μm and the thickness of 0.2 were formed on this conductive support in the same manner as in Example 2.
A μm charge generation layer was formed.

Then, the organosilicon compound synthesized in Synthesis Example 3 was synthesized.
100 parts of the synthesized triarylamine compound was dissolved in toluene 167
In 2 parts, add 2 parts of dibutyltin diacetate and mix.
Solution with an average particle size of 3 μm_TwoFine particles 1.25
Of the charge generating layer was added to the charge generating layer.
Coating was performed by the coating method. Dry at 120 ° C for 5 hours, heat hardened
To form a charge transport layer having a thickness of 10 μm. With a microscope
Observed SiO _TwoExcept for the particles, they are transparent and uniform.
Was.

The pencil hardness was 4H and the contact angle of water was 11
It was 0 degrees.

This electrophotographic photosensitive member was charged to -700 V, and the electrophotographic characteristics were measured using light having a wavelength of 680 nm. E _1/2 (exposure amount required to reduce the charging potential to -350 V) Was 0.23 μJ / cm ² and the residual potential was −21 V.

The electrophotographic photoreceptor was charged with an initial charge of -50 using the same Canon laser beam printer as in Example 2.
When the image was evaluated at 0 V, the abrasion of the photoreceptor after the durability test of 10,000 sheets was as small as 0.2 μm, the contact angle of water was as good as 102 °, and the injection of charge such as black spots and interference. There was no deterioration of the image due to the stripes, and the reproducibility of one pixel of the highlight portion in an input signal equivalent to 600 dpi was sufficient.

Example 4 In the same manner as in Example 1, a charge generation layer was formed.

Next, a solution prepared by adding 0.1 parts of silicone resin fine particles having an average particle size of 2 μm to the liquid for the charge transport layer used in Example 1 was dried on the charge generation layer by a dip coating method. Coating was performed so that the film thickness became 9 μm.

Next, 100 parts of 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- (triethoxysilyl) ethyl] benzene synthesized in Synthesis Example 3 was used as a surface protective layer in toluene. 167 parts were dissolved, and 2 parts of dibutyltin diacetate was added and mixed, and a mixed solution was applied by a spray coating method.

By drying and heat curing at 140 ° C. for 4 hours, a transparent and uniform surface protective layer having a thickness of 3 μm was formed. The pencil hardness was 2H and the contact angle of water was 115 degrees.

When the electrophotographic characteristics of this electrophotographic photosensitive member were evaluated in the same manner as in Example 1, the E1 _{/ 2} was 1.0 μJ.
/ Cm ² , the residual potential was as good as −25V.

Further, the electrophotographic photosensitive member was initially charged to -40 using the same digital full-color copying machine as in Example 1.
When the image was evaluated at 0 V, the abrasion loss after the durability test of 10,000 sheets was extremely small at 0.13 μm, the contact angle of water was 109 degrees, and the reproducibility of the highlight portion and the high density portion was obtained. Excellent image was obtained.

Example 5 In the same manner as in Example 2, a charge generation layer was formed.

Subsequently, 100 parts of the organosilicon-modified triarylamine compound synthesized in Synthesis Example 8 was added to toluene 167
The mixture was dissolved in 2 parts, and a solution obtained by adding 2 parts of dibutyltin diacetate and mixing was applied onto the charge generation layer by a dip coating method. After drying at 120 ° C. for 5 hours and heat curing, the photoreceptor of the present invention having a charge transport layer having a thickness of 10 μm was prepared.

The pencil hardness is 5H and the contact angle of water is 10
7 degrees.

When the electrophotographic characteristics were measured in the same manner as in Example 2, the E _1/2 was 0.20 μJ / cm ² and the residual potential was -25 V.

The image of this electrophotographic photosensitive member was evaluated at an initial charge of -500 V using the same laser beam printer as in Example 2. The abrasion loss after a 10,000-sheet endurance test was 0. The contact angle of water is 98 degrees, which is extremely small, and is 98 degrees, which is good. There is no deterioration of the image due to charge injection such as black spots and interference fringes. there were.

[0154]

As described above, according to the present invention, an electrophotographic photoreceptor having a uniform surface layer without light scattering or bleed and having both low surface energy and mechanical and electrical durability. And a process cartridge and an image forming apparatus having the electrophotographic photosensitive member.

[Brief description of the drawings]

FIG. 1 is a diagram showing a layer configuration of a first example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a diagram showing a layer configuration of a first example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a diagram showing a relationship between a light intensity distribution, a spot diameter, and a product of a light spot area and a thickness of a photosensitive layer.

FIG. 4 is a diagram illustrating a schematic configuration of a first example of the image forming apparatus of the present invention.

FIG. 5 is a diagram illustrating a schematic configuration of a second example of the image forming apparatus of the present invention.

FIG. 6 shows 4- [2- (triethoxysilyl) of Synthesis Example 1.
1 is an H-NMR spectrum of [ethyl] triphenylamine.

FIG. 7 is an H-NMR spectrum of 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- (triethoxysilyl) ethyl] benzene of Synthesis Example 3.

8 is a C-NMR spectrum of 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- (triethoxysilyl) ethyl] benzene of Synthesis Example 3. FIG.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Keiko Hiraoka, Inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Incorporated (72) Inventor ▲ Yoshi ▼ Kazuo Naga 3-10-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (18)

[Claims] An electrophotographic photoreceptor having a support and a photosensitive layer on the support, wherein the surface layer of the electrophotographic photoreceptor has the following formula (1): (A represents a hole transporting group, Q represents a hydrolyzable group or a hydroxyl group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group, and R ³ represents a substituted or unsubstituted alkylene group or arylene. M represents an integer of 1 to 3;
Represents a positive integer, and m × l is 3 or more. An electrophotographic photoreceptor comprising a resin obtained by polycondensing the organosilicon-modified hole transporting compound represented by the formula (1) as a monomer component. 2. The electrophotographic photoreceptor according to claim 1, wherein m is 3. 3. The electrophotographic photoreceptor according to claim 1, wherein the monomer component is only the organosilicon-modified hole transporting compound represented by the formula (1). 4. A is represented by the following formula (2). (R ⁴ , R ⁵ and R ⁶ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ⁴ , R ⁵ and R ⁶ are the same or different. The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein 5. The modified organosilicon hole-transporting compound.
5. The electrophotographic photoreceptor according to claim 1, which has an ionization potential of 5 to 6.2 eV. 6. The modified organosilicon hole transporting compound is 1 ×
The electrophotographic photosensitive member according to any one of claims 1 to 5 with a 10 ^-7 cm ² / Vsec or more drift mobility. 7. A process comprising: an electrophotographic photosensitive member; and at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit, and integrally supporting the electrophotographic photosensitive member and the at least one unit. In the cartridge, the electrophotographic photosensitive member is an electrophotographic photosensitive member having a support and a photosensitive layer on the support, and the surface layer of the electrophotographic photosensitive member has the following formula (1): (A represents a hole transporting group, Q represents a hydrolyzable group or a hydroxyl group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group, and R ³ represents a substituted or unsubstituted alkylene group or arylene. M represents an integer of 1 to 3;
Represents a positive integer, and m × l is 3 or more. A process cartridge comprising a resin obtained by polycondensing the organosilicon-modified hole-transporting compound represented by the formula (1) as a monomer component. 8. The process cartridge according to claim 7, wherein m is 3. 9. The process cartridge according to claim 7, wherein the monomer component is only the organosilicon-modified hole transporting compound represented by the formula (1). 10. A is a compound represented by the following formula (2). (R ⁴ , R ⁵ and R ⁶ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ⁴ , R ⁵ and R ⁶ are the same or different. The process cartridge according to any one of claims 7 to 9, wherein: 11. The process cartridge according to claim 7, wherein the modified organosilicon hole transporting compound has an ionization potential of 4.5 to 6.2 eV. 12. The modified silicon-transporting hole-transporting compound is one of
The process cartridge according to claim 7, having a drift mobility of × 10 ⁻⁷ cm ² / Vsec or more. 13. An image forming apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit and a transferring unit, wherein the electrophotographic photosensitive member has a support and a photosensitive layer on the support. Wherein the surface layer of the electrophotographic photoreceptor has the following formula (1): (A represents a hole transporting group, Q represents a hydrolyzable group or a hydroxyl group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group, and R ³ represents a substituted or unsubstituted alkylene group or arylene. M represents an integer of 1 to 3;
Represents a positive integer, and m × l is 3 or more. An image forming apparatus comprising a resin obtained by polycondensing the organosilicon-modified hole transporting compound represented by the formula (1) as a monomer component. 14. The image forming apparatus according to claim 13, wherein m is 3. 15. The electrophotographic apparatus according to claim 13, wherein the monomer component is only the organosilicon-modified hole transporting compound represented by the formula (1). 16. A is represented by the following formula (2): (R ⁴ , R ⁵ and R ⁶ are organic groups, at least one of which represents an aromatic hydrocarbon ring group or a heterocyclic group, and R ⁴ , R ⁵ and R ⁶ are the same or different. The image forming apparatus according to any one of claims 13 to 15, wherein 17. The image forming apparatus according to claim 13, wherein the modified organosilicon hole transporting compound has an ionization potential of 4.5 to 6.2 eV. 18. The modified organosilicon hole transporting compound is one of
The image forming apparatus according to claim 13, wherein the image forming apparatus has a drift mobility of × 10 ⁻⁷ cm ² / Vsec or more.