JPH0721644B2 - Photoconductive member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a novel function-separated laminated electrophotographic photoreceptor,
In particular, it relates to a photoconductive member used for a photoconductor.

"Problems to be Solved by Conventional Techniques and Inventions" Generally, electrophotographic photoreceptors are roughly classified into a single layer type and a function separation type laminated type. As a single layer type, Se type,
CdS-based, ZnO-based, PVK / TNF-based, pyrylium-chlorine, and recently amorphous silicon-based. The single-layer type needs to excel in both functions because one layer has both optical carrier generation and transport, but such a material has not been easily found.

For this reason, in recent years, there have been 2
A function-separated multi-layer type photoconductor having three different functions has been developed. Examples of the charge generation layer include Se-based, chlorodian blue-based, squarerium-based, azo pigment-based, phthalocyanine-based, pyrylium salt-based, and the like, and the charge-transporting layer includes PVK, pyrazoline-based, hydrazone-based, cyclohexane-based, Etc.

Among the above materials, the low molecular weight organic semiconductor is usually used by dispersing it in an insulating resin.

However, conventionally, there has been a problem that any charge generation layer has a low photocarrier generation efficiency (quantum efficiency), and thus a low photosensitivity. In addition, each charge transport layer has a drawback that the transport efficiency (drift mobility) of photogenerated carriers is low.

In addition, since the above-mentioned charge generation layer is generally a micron-order thin layer, it has low mechanical strength and it is difficult to provide the charge generation layer on the surface. Therefore, it is general to provide a charge transport layer as an upper layer and a charge generation layer as a lower layer. Since the holes that generally control the conduction of the charge transport layer are holes, the charge polarity of the laminated photoreceptor is negative.

However, if the photoreceptor is used with negative charging, problems such as ozone generation and charging instability during corona charging are likely to occur, which may be practically inconvenient.

An object of the present invention is to provide a photoconductive member that can obtain a good image when used as an electrophotographic photoreceptor.

"Means and Actions for Solving Problems" First Invention The first invention of the present invention has been made in order to improve the above-mentioned drawbacks of the prior art. Both the charge generation layer and the charge transport layer have the above-mentioned materials. Is not used at all.

That is, as the charge generation layer, an amorphous silicon layer,
(However, the resin-dispersed charge generation layer is excluded; hereinafter abbreviated as a-Si: H layer).
10-75% by weight of N, N'-diphenyl-N, N'-bis (3-
Methylphenyl)-(1,1'-biphenyl) -4,4'-
A layer in which a diamine is dispersed is used.

Further, in order to prevent surface abrasion of the charge transport layer, it is preferable to stack a transparent protective layer in which a metal or metal oxide having an average particle size of 0.3 μm or less is dispersed in a transparent insulating resin.

The photoconductive member of the first invention preferably charges a negative charge on the charge transport layer through the transparent protective layer and neutralizes the negative charge on the charge transport layer with holes photogenerated from the charge generation layer. To form a latent image.

The a-Si: H layer is formed by glow discharge method (RF, DC), sputtering method, ion plating method, or the like.
Of the above methods, the glow discharge method is preferable because the control for forming the a-Si; H layer having the desired characteristics is relatively easy.

To make the a-Si: H layer P-type, B and A of Group III of the periodic table are used.
The addition of l, Ga, In, Tl, etc. is preferable.

When forming an a-Si: H layer by the glow discharge method, SiH ₄ , Si ₂ H
Glow discharge of hydrogenated silicon gas such as ₆ decomposes the hydrogenated silicon gas to form an a-Si: H layer on the support. The silicon hydride gas may be used after diluting it to an appropriate amount with H ₂ , Ar or the like. The content of hydrogen atoms is usually 10-40 at
It is omic%, preferably 15 to 30 atomic%.

When it is desired to use P type, B ₂ H ₆ together with the above hydrogenated silicon gas
It suffices to introduce gas such as. The addition ratio of B ₂ H ₆ gas or the like to the silicon hydride gas is preferably 1 to 50 Vppm.

In addition to the silicon hydride gas, these derivative gases can also be used as the raw material gas.

As RF or DC power source for glow discharge, usually 100 to 2
A voltage of 000V, preferably 300 to 1500V, is good, and electric power is usually 0.1 to 300W, preferably 0.5 to 100W. In the case of RF, the frequency is usually 0.2-30MHz, preferably 5-20MH
z is good. The substrate temperature is preferably 200 to 300 ° C.

The support should preferably be any suitable electrical conductor. Suitable conductors include aluminum, copper, graphite, dispersed conductive salts, conductive polymers and the like. The support can be rigid or flexible and can be of any thickness. Typical supports include flexible belts or sleeves, sheets, webs, plates, cylinders, drums. The support may also consist of a composite structure such as plastic coated with a thin conductor layer such as aluminum or copper iodide, or glass coated with a thin conductive coating layer of chromium or tin oxide. .

Examples of the insulating resin used for the charge transport layer laminated on the a-Si: H layer include polycarbonate, acrylic ester polymer, vinyl polymer, cellulose polymer, polyester, polysiloxane, polyamide, polyurethane and epoxy, and Examples thereof include block, random, alternating, and graft copolymers. A preferred insulating resin is polycarbonate resin. The preferred molecular weight is about 20,000 to about 100,000, more preferably about 50,000 to about 100,000.

The most preferable material for the insulating resin is poly (4,4′-) having a molecular weight of about 35,000 to about 40,000, which has been discovered as LEXON 145 (Loxon145) by General Electric Company.
Isopropylidene-diphenylene carbonate); poly (4,4'-isopropylidene-diphenylene carbonate) having a molecular weight of about 40,000 to about 45,000, marketed as Lexan 141 by General Electric Co .; AG (Farben fabricken B
a polycarbonate resin having a molecular weight of about 50,000 to about 100,000, marketed as Makrolon by Ayer AG, and Marlon by Mopei Chemicals.
n) with a molecular weight of about 20,000 to about 50,000
Is a polycarbonate resin.

The formula of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is as follows.

As described above, the charge transport layer contains about 10 to 75% by weight of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) in the polycarbonate resin.
A layer in which -4,4'-diamine is dispersed is preferable. Although the charge transport layer is substantially non-absorbent to flexible light, it allows the injection of holes generated from the charge generation layer and moves these holes through the active charge transport layer to cause this charge to migrate. It is "active" in that it can selectively dissipate the surface charge on the surface of the transport layer.

The photoconductive member according to the first aspect of the present invention comprises an a-Si: H layer as a charge generating layer on a support, and an insulating resin such as a polycarbonate resin as a charge transporting layer containing about 10 to 75% by weight of N, N '. -Diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine dispersed layer is laminated.

It has been found that a thickness of the charge generation layer of about 0.05 to 20 μm is satisfactory, and good results are obtained at a thickness of about 0.2 to 5 μm. The thickness of the charge transport layer is preferably about 5 to 100 μm, but thicknesses outside this range can be used.

The photoconductive member of the first aspect of the present invention has high photosensitivity and rich panchromaticity because it uses an a-Si: H layer as the charge generation layer, as compared with the prior art. Further, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was used as a low molecular weight organic semiconductor in the charge transport layer. Therefore, the carrier (hole) transportation efficiency is high and it is suitable for high-speed copying machines.

Further, in a preferred aspect of the first aspect of the present invention, the average particle size in the transparent insulating resin is 0.3 μm on the photoconductive member.
By laminating a transparent protective layer in which the following metal or metal oxide is dispersed, surface abrasion of the charge transport layer can be suppressed.

As a metal or metal oxide, the volume resistivity is 10
Any metal or metal oxide powder can be used as long as it has an average particle size of ¹¹ Ω · cm or less and an average particle size of 0.3 μm or less. Examples thereof include metals such as gold, silver, aluminum, iron, copper and nickel, and metal oxides such as zinc oxide, titanium oxide, tin oxide, bismuth oxide, indium oxide and antimony oxide. At this time, several kinds of metals and metal oxides may be mixed and used. Particularly preferred is an average particle size of 0.15 containing tin oxide and antimony oxide.
It is a powder of μ or less.

As the transparent insulating resin, one that is substantially transparent to visible light and is excellent in electrical insulation, mechanical strength, and adhesiveness is desirable. For example, polyester resin, polycarbonate resin, polyurethane resin, epoxy resin, acrylic resin,
A vinyl chloride-vinyl acetate copolymer, a silicone resin, an alkyd resin, a polyvinyl chloride resin, a cyclized butadiene rubber, a fluororesin or the like can be used. When the dissolution resistance of the protective layer is required, it is desirable to use a curable resin.

The composition ratio of the resin and the metal or metal oxide in the protective layer is 5 to 5 with respect to 100% by weight of the resin.
It is used in an amount of 00% by weight, preferably 5 to 100% by weight.
The thickness of the protective layer can be set between 1 and 30 μm as required.

On the other hand, a carrier blocking layer may be provided between the support and the charge generation layer (a-Si: H layer).

Since the photoconductive member of the first invention is used as an electrophotographic photosensitive member by negative charging, it is sufficient to spin injection of holes as the carrier blocking layer, and to provide an n-type a-Si: H layer. Good. The n-type a-Si: H layer may be formed by introducing a gas such as PHz of Group V of the periodic table together with SiH ₉ , Si ₂ H _{6 and the} like in the glow discharge method. The addition ratio of PH ₃ gas or the like to the silicon hydride gas is appropriately 50 to 1000 Vppm, 50 to 500 V
ppm is preferred. Further, the a-Si: H layer formed by the glow discharge method also functions as a carrier blocking layer. The thickness of the n-type layer is preferably 0.1 to 1 μm, and a-Si:
The thickness of the H layer is preferably 0.01 to 0.1 μm.

Second Invention The second invention has been made to improve the above-mentioned drawbacks of the prior art, and provides a photoconductive member of a laminated electrophotographic photosensitive member that can be used in positive charging. Moreover, the charge transporting layer and the charge generating layer do not use the above-mentioned materials, and the charge transporting layer has about 10 to about 10% in the insulating resin.
A layer in which 75% by weight of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was dispersed was used as a charge generation layer. Is a stack of amorphous silicon layers (excluding the resin dispersion type charge generation layer).

Further, it is preferable that a surface protective layer made of hydrogenated amorphous silicon containing at least one kind of nitrogen atom, carbon atom or oxygen atom is laminated on the laminated photoreceptor.

In the photoconductive member of the second invention, preferably, a positive charge is charged on the charge generation layer through the surface protective layer, electrons photogenerated in the charge generation layer neutralize the surface charge, and holes transport charge. The latent image is formed by passing through the layer to the support.

In the description of the second invention, description of the same components as those in the first invention will be omitted.

The photoconductive member according to the second aspect of the present invention comprises a support, a charge transport layer, and an insulating resin such as a polycarbonate resin containing about 10 to 75% by weight of N, N'-diphenyl-NN'-bis (3-methylphenyl). )-(1,1'-biphenyl) -4,4'-diamine is dispersed in the layer, and an a-Si: H layer is laminated as a charge generation layer.

The thickness of the charge transport layer should be about 5-100 μm, although thicknesses outside this range can be used. The thickness of the charge generation layer has been found to be satisfactory at about 0.05 to 20 μm, and good results are obtained at a thickness of about 0.2 to 5 μm. However, it must be thinner than the carrier range of holes, or it will cause a residual potential.

Since the photoconductive member of the second aspect of the present invention can be used with positive charging as compared with the prior art, various problems when using negative charging can be avoided. Furthermore, since the a-Si: H layer is used for the charge generation layer, it has high photosensitivity and is rich in panchromaticity. In addition, as a low molecular weight organic semiconductor in the charge transport layer, N, N'-
Diphenyl N, N'-bis (3-methylphenyl)-(1,
Since 1'-biphenyl) -4,4'-diamine is used, it has a high carrier (hole) transport efficiency and is suitable for high-speed copying machines.

Furthermore, in a preferred aspect of the second aspect of the present invention, a surface protective layer made of hydrogenated amorphous silicon containing at least one atom of nitrogen atom, carbon atom, or oxygen atom on the photoconductive member. By stacking
It is possible to prevent a decrease in image density, image blurring, and flow due to surface deterioration peculiar to the a-Si: H layer.

The surface protection layer is the same as the charge generation layer in the glow discharge method (RF, D
C), sputtering method, ion plating method, etc. Among the above methods, among the above methods, it is relatively easy to control to form a layer having desired properties.
The glow discharge method is often used.

The discharge conditions are the same as those used in forming the a-Si: H layer described above, and a raw material gas containing nitrogen atoms, carbon atoms, or oxygen atoms as constituent atoms is introduced together with the silane or silane derivative gas described above. On the a-Si: H layer, a- (Si _x1 N _1-x1 ) _x2 H _1-x2 , a- (S
i _y1 C _1-y1 ) _y2 H _1-y2 , or a-Si _z1 O _1-z1 ) _z2 H _1-z2, etc. are prepared. The a-Si: H layer and the surface protective layer are
It can be formed continuously without breaking the vacuum.

When forming the a- (Si _x1 N _1-x1 ) _x2 H _1-x2 layer, it is necessary to introduce a gas having nitrogen atoms as constituent atoms together with the above-mentioned silane or silane derivative gas as a source gas.

As a starting material having a nitrogen atom as a constituent atom, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ),
Gaseous nitrogen such as hydrogen azide (HN ₃ ) and ammonium azide (NH ₄ N ₃ ) or nitrogen compounds such as nitrogen and azide that can be gasified are considered.

When forming an a- (Si _y1 C _1-y1 ) _y2 H _1-y2 layer, the raw material gas together with the silane or silane derivative gas described above,
It is necessary to introduce a gas having carbon atoms as constituent atoms.
The gas has carbon atoms and hydrogen atoms as constituent atoms.

Methane (H _4), ethane (C ₂ H _6), propane (C ₃ H _8), n
- butane _{(n-C 4 H 10)} , pentane (C ₅ H ₁₂₎ saturated hydrocarbons, such as ethylene (C ₂ H _4), propylene (C ₃ H _6), butene -1 (C ₄ H _8), Butene-2 (C ₄ H ₈ ) isobutylene (C ₄
H ₈ ), pentene (C ₅ H ₁₀ ) and other ethylene hydrocarbons, acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ) and other acetylene hydrocarbons, etc. is there.

On the other hand, there are also alkylsilicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

When forming the a- (Si _z1 O _1-z1 ) _z2 H _1-z2 layer, it is necessary to introduce a gas containing oxygen atoms as constituent atoms into the plasma together with the silane or silane derivative gas described above as a source gas. is there.

For example, oxygen (O ₂ ), ozone (O ₃ ), carbon monoxide (C
O), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), trinitrogen dioxide (N
₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentaoxide (N
₂ O ₅ ), Nitric oxide (NO ₃ ), Disiloxane (H ₃ SiOSi
H ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) and the like.

Two or more kinds of the above-mentioned gases containing nitrogen atoms, carbon atoms and oxygen atoms as constituent atoms may be used as the source gas.

The composition ratio of the a- (Si _x1 N _1-x1 ) _x2 H _1-x2 layer is such that x ₁ is usually 0.43 to 0.6, preferably 0.43 to 0.5, and x ₂ is usually
It is set to 0.65 to 0.98, preferably 0.7 to 0.95.

The composition ratio of the a- (Si _y1 C _1-y1 ) _y2 H _1-y2 layer is, as y ₁ , usually 0.1 to 0.5, preferably 0.1 to 0.35, optimally 0.15 to 0.3,
As y ₂ , usually 0.60 to 0.99, preferably 0.65 to 0.98,
The optimum value is 0.7 to 0.95.

The composition ratio of the a- (Si _z1 O _1-z1 ) _z2 H _1-z2 layer is, as z ₁ , usually 0.33 to 0.40, preferably 0.33 to 0.37, and as z ₂ , usually 0.65 to 0.98, It is preferably 0.70 to 0.95.

The film thickness of each layer is preferably 0.01 to 0.2 μm.

As described above, by forming the surface protective layer on the charge generation layer, the decrease in the image density due to the aging of the charge potential due to the surface oxidation of the charge generation layer or the decrease due to the xerographic cycle, the blurring of the image, and the flow of the image. Etc. can be prevented.

On the other hand, a carrier blocking layer or an adhesive layer may be provided between the support and the charge transport layer. The carrier blocking layer material includes a silane coupling agent, nylon, epoxy, aluminum oxide and the like, and the adhesive layer material includes an insulating resin binder such as polyester as described above. The thickness of both the carrier blocking layer and the adhesive layer is preferably 0.01 to 0.1 μm, and the support, the carrier blocking layer, the adhesive layer, and the charge transport layer are laminated in this order.

[Examples] Examples of the first invention Next, on a support for a photoconductive member, an amorphous silicon-based charge generation layer containing silicon atoms, hydrogen atoms and atoms of Group III of the periodic table, an insulating resin. About 10 to 75% by weight of N, N'-
Diphenyl-N, N'-bis (3-methylphenyl)-
Examples of the photoconductive member of the first aspect of the present invention are described below, which are characterized in that charge transport layers in which (1,1'-biphenyl) -4,4'-diamine is dispersed are sequentially laminated. To do. Further, an example in which a transparent protective layer in which a metal or metal oxide having an average particle size of 0.3 μm or less is dispersed in a transparent insulating resin is laminated on the photoconductive member will be described.

Example 1 A mixed gas of silane (SiH ₄ ) gas, hydrogen gas and diborane (B ₂ H ₅ ) gas was formed on a cylindrical substrate by using a capacitively coupled plasma CVD apparatus capable of forming an amorphous silicon film. An amorphous silicon film was formed on the cylindrical Al substrate by glow discharge decomposition. The generation conditions at this time were as follows.

A cylindrical Al substrate is installed at a predetermined position in the reaction chamber of the plasma CVD apparatus, the substrate temperature is maintained at a predetermined temperature of 250 ° C., 100% silane gas is 100 cc / min, and hydrogen gas is 89 cc / min in the reaction chamber. After flowing diborane gas diluted with hydrogen at 11 cc / min to maintain the internal pressure of the reactor at 0.57 Torr, 1
High-frequency power of 3.56MHz was applied to cause glow discharge, and the output of the high-frequency power supply was maintained at 85W. In this way, a charge generation layer having a thickness of 2 μm was formed on the cylindrical Al substrate.

Next, 5 g of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine powder and Macrolone from Farben Fabryken Bayer AG Polycarbonate resin powder (5 g), which was sold as, was placed in a flask containing 50 g of methylene chloride, stirred and dissolved to form a homogeneous dispersion liquid. This dispersion was applied on the charge generation using an ablizer,
The film was dried under the condition of ° C / hr to form a charge transport layer having a film thickness of 25 µm and formed into a laminated structure.

Incidentally, FIG. 1 shows a photoconductive member according to Example 1, and in FIG. 1, 1 is a charge transport layer, 2 is a charge generation layer, 3 is a support, and 4 is a photoconductive member. is there.

As a result of the evaluation of the electrophotographic characteristics of the electrophotographic photosensitive member, the applied potential of −6 KV, the charging potential is 760 V, the residual potential is 1
About 1 Luxsec was obtained at 0 V and a half-exposure sensitivity. Furthermore, after 1K cycle, the charging potential is 770V, the residual potential is 20V,
The sensitivity was about 1 luxsec at the half exposure.

As expected from the above data, 1st cycle, 1K
A clear and good image with no fog was obtained at every cycle.

Example 2 This second example provides a photoconductive member having a carrier blocking layer provided between the support and the charge generation layer (a-Si: H layer) in the photoreceptor prepared in Example 1. To do. Then, in the same manner as in Example 1, the glow discharge method was used to obtain 100% silane at 7 cc / min and ammonia gas at 35 c / min.
c, Nitrogen gas is introduced at 200 cc / min, and the inside of the reaction tank is 0.5 Tor
After maintaining the internal pressure of r, high-frequency power of 13.56MHz was applied to cause glow discharge, and the output of the high-frequency power supply was 70W.
Maintained at. In this way, the thickness on the cylindrical Al substrate
A carrier blocking layer made of 550Å silicon nitride was created. The charge generation layer and the charge transport layer were formed in the same manner as in Example 1.

Note that FIG. 2 shows a photoconductive member according to Example 2, and in FIG. 2, 5 is a carrier blocking layer.

When the characteristics of the electrophotographic photosensitive member were evaluated, −
With an applied voltage of 6 KV, the charging potential was 810 V, the residual potential was 15 V, and the sensitivity was about 1 lux sexc at half-exposure. Furthermore, after 1 K cycle, the charging potential was 830 V, the residual potential was 30 V, and the sensitivity was about 1 luxsec at a half exposure. As expected from the above data, clear and fog-free good images were obtained in both the first cycle and the 1Kth cycle.

Comparative Example 1 N, N′-diphenyl-in the charge transport layer in Example 2
N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4 'diamine was added to N, N'-diphenyl-N, N'
A photoconductive member was prepared in the same manner as in Example 2 except that -bis (2-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was used instead. When the characteristics of the electrophotographic photosensitive member were evaluated, an applied voltage of −6 KV, a charging potential of 810 V, a residual potential of 50 V, and a sensitivity of 1.2 lu at a half exposure amount.
I got about xsec. Furthermore, after 1K cycle, the charging potential is 83
0V, residual potential 70V, sensitivity about 1.2luxsec. Fog, which is considered to be due to the residual potential, occurred at the 1K cycle.

Comparative Example 2 N, N'-diphenyl-in the charge transport layer in Example 2
N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was replaced with N, N'-diphenyl-N,
A photoconductive member was prepared in the same manner as in Example 2, except that N'-bis (4-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was used. When the characteristics of the electrophotographic photosensitive member were evaluated, the applied potential was −6 KV, the charging potential was 810 V, the residual potential was 10 V, and the sensitivity was 1.0 at a half-exposure amount.
got about luxsec. Furthermore, after 1K cycle, the charging potential
850V, residual potential 70V, sensitivity about 1.2luxsec. 1K
At the cycle, fogging that is considered to be due to the residual potential occurred.

Example 3 This third example provides a photoconductive member in which a transparent protective layer is laminated on the photoconductive member prepared in Example 2. MITSUBISHI METALS tin oxide with an average particle size of 0.1 μm /
14 g of antimony oxide fine powder and 4 g of tan from Kansai Paint
20.9 g of polyacrylurethane resin powder sold as 000 was put in a ball mill containing 44.1 g of methylene chloride, and the ball mill was rotated and stirred to be dissolved to obtain a homogeneous dispersion liquid. After making a homogeneous dispersion, transfer it to a flask and use Desmodur TPL-5-229 from Sumitomo Bayer Wetan.
5.1g hardener sold as 1 and 632g methylene chloride
Was added, and the mixture was stirred with a magnetic stirrer and dissolved to form a homogeneous dispersion.

This dispersion was applied onto the photoconductive member prepared in Example 2 using an applicator and dried under the conditions of 80 ° C. for 24 hours to prepare a transparent protective layer having a film thickness of 2 μm, and to form a laminated structure. did.

Incidentally, FIG. 3 shows a photoconductive member according to Example 3, and in FIG. 3, 6 is a transparent protective layer.

The characteristics of the electrophotographic photosensitive member were evaluated. as a result,
With applied voltage of −6KV, charging potential is 790V, residual voltage is 20V,
The sensitivity was about 1 luxsec at the half exposure. After 1 K cycle, the charging potential was 820 V, the residual potential was 50 V, and the sensitivity was about 1 luxsec at the half exposure.

As expected from the above data, 1st cycle, 1K
A clear and good image with no fog was obtained at every cycle.

Second invention Next, on the support for the photoconductive member, about 10
~ 75 wt% N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine dispersed charge transport layer, silicon atom Examples of the photoconductive member of the second invention of the present invention are characterized in that an amorphous silicon-based charge generation layer composed of an oxygen atom and an atom of Group III of the periodic table is sequentially laminated. Explained. An example in which a surface protective layer made of amorphous silicon containing at least one kind of nitrogen atom, carbon atom, or oxygen atom is laminated on the photoconductive member will also be described.

Example 4 N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine powder
5g and polycarbonate resin powder sold by Farben Fabryken Bayer AG as Macrolon
5 g and 5 g were placed in a flask containing 50 g of methyl chloride, stirred and dissolved to form a homogeneous dispersion liquid.

This dispersion was applied onto a cylindrical Al substrate using a spray and dried at 80 ° C./hr to form a charge transport layer having a film thickness of 25 μm.

This cylinder was placed in a capacitively coupled plasma CVD device capable of forming an amorphous silicon film on a cylindrical substrate.
Exhausted to below ^-5 Torr. Then, set the cylinder temperature to 100 ° C.
Then, a mixed gas of 100% silane gas 120SCCM, hydrogen diluted 100ppm diborane gas 20SCCM, and 100% hydrogen gas 90SCCM was introduced into the reaction chamber. Then, the pressure inside the reaction chamber was maintained at 0.4 Torr. After that, 13.56MHz 60W high frequency power was applied to keep the discharge for 20 minutes. That is, by decomposing this mixed gas by glow discharge, a charge generation layer made of a photoconductive amorphous silicon film containing hydrogen and a slight amount of boron was laminated on the charge transport layer to a film thickness of 1 μm.

Incidentally, FIG. 4 shows a photoconductive member according to Example 4. In FIG. 4, 11 is a charge generation layer, 12 is a charge transport layer, 13 is a support, and 14 is a photoconductive member. is there.

When the above photoconductive member drum was put in a copying machine and the image quality was evaluated by a positive corona charging method, a clear and good image free from fogging was obtained. Further, when the copying was repeated 10,000 times, no decrease in image density was observed.

Example 5 The same method as in Example 4 was applied, a charge transport layer was applied, a charge generation layer was laminated thereon, and then the reaction chamber was evacuated to 10 ^-5 Torr or less. Next, keep the temperature of the cylindrical substrate at 100 ° C and use silane gas 1
Gas was introduced at a flow rate of 0 SCCM, 50 SCCM of ammonia gas, and 200 SCCM of nitrogen gas, and the pressure in the reaction chamber was maintained at 1.0 Torr. After that, 13.56MHz, 100W high frequency power was applied to keep the discharge for 30 minutes. That is, the surface protection layer made of an amorphous silicon nitride film containing hydrogen is formed on the charge generation layer by decomposing this mixed gas by glow discharge.
The layers were laminated at 0.5 μm.

Incidentally, FIG. 5 shows a photoconductive member according to Example 5, and in FIG. 5, 15 is a surface protective layer.

When the photoconductive member drum was placed in a copying machine and the image quality was evaluated by a positive corona charging method, a clear and good image free from fogging was obtained. Further, when the copying was repeated 50,000 times, no decrease in image density was observed.

Example 6 A charge transport layer was applied in the same manner as in Example 4, a charge generation layer was laminated thereon, and then the reaction chamber was evacuated to 10 ⁻⁵ Torr or less. Next, the temperature of the cylindrical substrate was kept at 100 ° C., the mixed gas was introduced at each flow rate of 50 SCCM of silane gas, 50 SCCM of methane gas and 100 SCCM of hydrogen gas, and the pressure inside the reaction chamber was maintained at 0.5 Torr. Then, 13.56MHz, 120W high frequency power was applied to sustain the discharge for 30 minutes. That is, by decomposing this mixed gas by glow discharge, a surface protective layer made of an amorphous silicon carbide film containing hydrogen was laminated on the charge generation layer to a thickness of 0.5 μm.

Note that this has the same configuration as in FIG.

When the above photoconductive member drum was put in a copying machine and image quality was evaluated by a positive corona charging method, a clear and good image quality without fog was obtained. Further, when the copying was repeated 50,000 times, no decrease in image quality density was observed.

"Effects of the Invention" As described above, according to the present invention, a good image can be obtained when used as an electrophotographic photoreceptor.

In the first aspect of the present invention, a surface protective layer composed of hydrogenated amorphous silicon containing at least one kind of nitrogen atom, carbon atom, or oxygen atom may be laminated on the photoconductive member. Well, in the second invention,
The average particle size is 0.3μ in the transparent insulating resin on the photoconductive member.
A transparent protective layer in which a metal or metal oxide of m or less is dispersed may be laminated.

[Brief description of drawings]

FIG. 1 is a structural explanatory view showing a photoconductive member according to Embodiment 1 of the first invention, FIG. 2 is a structural explanatory view showing a photoconductive member according to Embodiment 2 of the first invention, and FIG. FIG. 4 is a structural explanatory view showing a photoconductive member according to a third embodiment, FIG. 4 is a structural explanatory view showing a photoconductive member according to a fourth embodiment of the second invention, and FIG. 5 is according to the fifth and sixth embodiments of the second invention. It is a structure explanatory view showing a photoconductive member. 1 ... Charge transport layer, 2 ... Charge generation layer, 3 ... Support,
4 ... Photoconductive member, 5 ... Carrier blocking layer, 6
...... Transparent protective layer, 11 …… Charge generating layer, 12 …… Charge transporting layer, 13 …… Support, 14 …… Photoconductive member, 15 …… Surface protective layer.

Front page continuation (72) Inventor Tokuyoshi Takahashi 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Zero Tux Co., Ltd., Takematsu Works (72) Inventor Masayuki Nishikawa 1600 Takematsu, Minamiashigara, Kanagawa Fuji Zero Tux, Takematsu Works ( 56) References JP-A-56-60446 (JP, A) JP-A-56-35140 (JP, A) JP-A-55-79450 (JP, A) JP-A-53-27033 (JP, A)

Claims (4)

[Claims] 1. An amorphous silicon-based charge generation layer containing silicon atoms, hydrogen atoms and atoms of Group III of the periodic table on a support for a photoconductive member (excluding a resin dispersion type charge generation layer). ), 10 to 75% by weight of N, N'-diphenyl-N, in the insulating resin,
A photoconductive member comprising a charge transport layer having N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine dispersed therein, which are sequentially laminated. 2. The photoconductive member according to claim 1, wherein a metal or metal oxide having an average particle size of 0.3 μm or less is contained in the transparent insulating resin on the photoconductive member. A photoconductive member comprising a laminated transparent protective layer dispersed therein. 3. A support for a photoconductive member, comprising 10 to 75% by weight of N, N'-diphenyl-N, in an insulating resin.
N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine-dispersed charge transport layer, containing silicon atom, hydrogen atom and Group III atom of the periodic table A photoconductive member comprising an amorphous silicon-based charge generation layer (excluding a resin-dispersed charge generation layer) sequentially laminated. 4. The photoconductive member according to claim 3, wherein the photoconductive member has a hydrogenation containing at least one atom selected from a nitrogen atom, a carbon atom, and an oxygen atom on the photoconductive member. A photoconductive member characterized by being formed by laminating a surface protective layer made of amorphous silicon.