JPS62148968A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve the sensitivity of a photosensitive body by laminating an intermediate layer having a prescribed compsn. and essentially consisting of a carbon film and photoconductive layer thereon onto a conductive layer thereby improving the adhesiveness between the photoconductive layer and the substrate, suppressing the injection of electric charge from the substrate and decreasing residual potential. CONSTITUTION:The photosensitive body consists of at least the photoconductive layer and the intermediate layer (under coat layer) formed between the photoconductive layer and the substrate. The intermediate layer consists essentially of the carbon film, contains 0.1-6.7atomic% hydrogen (C:H) and is subjected to a polarity adjustment by incorporating group IIIA or VA elements therein. The hydrogen content in the intermediate layer is 1-67(atomic)%. The hydrogen content to additionally improve the adhesiveness and strain resistance is 40-67%, more preferably 45-65%, more particularly preferably 40-60%. B, Al, Ga, In, and B (particularly preferable) are usable as the group IIIA elements and P (particularly preferable), As, and Sb are usable as the group VA elements.

Description

[Detailed description of the invention] Industrial applications The present invention relates to photoreceptors, particularly electrophotographic photoreceptors.

Since the invention of the Carlson method, the application field of electrophotography has continued to make remarkable progress, and various materials have been developed and put into practical use for electrophotographic photoreceptors.

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, l-liphenylamine compounds, hydrazone compounds, sudyryl compounds, pyrazoline compounds,
Examples include organic substances such as oxadiazole compounds and oxadiazole compounds.

In addition, the configurations include a single-layer structure in which these substances are used alone, a binder-type structure in which they are dispersed in a binder, and a laminated structure in which a charge generation layer and a charge transport layer are provided for each function. Can be mentioned.

However, the conventionally used electrophotographic photoreceptor materials each have drawbacks.

One of them is their toxicity to the human body, but all inorganic substances, except for the amorphous silicon mentioned above, have unfavorable properties.

In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, neutralization, and cleaning. However, all of the above-mentioned mechanical materials lack durability and have many unstable performance factors.

In order to solve such problems, in recent years, amorphous silicon (hereinafter abbreviated as a-3i) manufactured by plasma chemical vapor deposition method (hereinafter referred to as plasma CVD method) has been used for photoreceptors, especially electrophotographic photoreceptors. It has been adopted.

A-8i sensitivity has various excellent properties. But a
-9i has a large relative dielectric constant ε of about 12, so in order to obtain a sufficient surface potential as a photoreceptor, essentially at least 25
There is a problem in that a film thickness of approximately μm is required. a-3
In the plasma CVD method, the deposition rate of the film is slow, so it takes a long time to produce the film.
The longer the preparation time, the more difficult it becomes to obtain -S i. As a result, the a-3i photoreceptor has drawbacks such as a high probability of image defects such as white spot noise and high raw material costs.

Although various attempts have been made to improve the above-mentioned drawbacks, it is essentially undesirable to make the film thickness greater than -v.

On the other hand, in the case of a-8i bad exposure, the density between the substrate and a-3i is i'''1
It also has drawbacks such as poor corona resistance and environmental resistance (and poor chemical resistance).

In order to solve such problems, it has been proposed to provide an organic plasma polymerized film as the under-to-1 layer of the A-9I photoreceptor (for example, JP-A-60-63541, JP-A-59-136742'; Public notices, etc.).

Organic plasma polymerized films can be prepared from all kinds of A-number ratio gases such as ethylene gas, benzene, and aromatic silanes (e.g., Ni, T, Hel).
), M Tsuen (M, 5hOn) et al.
of Applied Polymer Science (Jouna)
l of Applied Polywu! r Sci
+:nct, Volume 17, 885-892 (1973
2007), etc.), but it is known that
Plasma-polymerized films are used only in applications that require insulation. Therefore, their removal (like ordinary polyethylene films, they are considered to be insulating films with an electrical resistance of about <10" Ω cm, or at least are used with the understanding that they are such films). child.

On the other hand, in recent years, thin films of diamond-like carbon have been proposed in the semiconductor field, but nothing is known about their charge transport properties.

JP-A No. 60-63541 discloses a photoreceptor using a diamond-like film of 200 to 2 μm as an a-8i undercoat layer, but the film is
The purpose is to improve the adhesion of -3i. The polymeric membrane can be very thin, and charges move through the membrane by tunneling. This technique does not describe anything about preventing charge injection from the substrate.

Japanese Patent Application Laid-open No. 59-136742 discloses that about 5μ
A semiconductor device is disclosed in which an organic plasma polymerized film and a silicon film of m are sequentially formed. However, although the purpose of this organic plasma polymerized film is to prevent diffusion of aluminum, which is a substrate, into a-Si, there is no mention of its manufacturing method, film quality, etc. Furthermore, charge injection from the substrate occurs, resulting in a decrease in dark decay.

As mentioned above, conventionally it has been proposed to use an insulating organic plasma polymerized film or a diamond-like film for the undercoat layer, but the movement of charge due to these is basically due to tunneling effect and electrical breakdown phenomenon. This is due to

That is, the tunnel effect occurs when electrons pass through an insulating layer having an extremely small thickness (generally about 711 angstroms thick).

On the other hand, electrical breakdown occurs when a small amount of charge carriers in a layer are accelerated by an electric field and acquire enough energy to ionize atoms of the insulator, and the ionization increases the number of carriers and the same process repeats. This is a phenomenon in which the number of carriers increases in a rat-like manner, which occurs in the case of extremely high electric fields (generally 100 V/7zz or higher).

For example, in the case of a photoreceptor structure in which an insulator and a semiconductor are laminated,
Charges generated in the semiconductor (J electric field travels through the film, but cannot pass through the insulator at low electric fields. If the insulating layer is thin, this can be ignored as a surface potential, or it can be ignored in electrophotography. Additionally, since the effect on so-called development characteristics is extremely small, deterioration of characteristics due to the presence of the insulating layer does not pose a problem.Next, consider the effect of repeated use.

Charges accumulate in the insulating layer through repeated use, but once a high electric field (for example, 100 V/μM or more) is achieved due to the accumulated charges, no further electric field is applied due to electrical breakdown.

For example, when insulating materials that cause electrical breakdown at 100 V/μm are laminated to a thickness of 0.11 m, the so-called residual potential rise due to the insulating layers is only IOV even when repeated.

For the following two reasons, if a general insulating material is used for the photoreceptor, the film thickness must be less than approximately 5 μR. Otherwise, in IJ, the increase in residual potential due to the insulating layer will be 500 μR or less.
This results in fogging of the copied image, making it unusable.

As mentioned above, organic polymer films conventionally used in photoreceptors have been used as undercoat layers21, but these are films that do not require the transport function of a gear carrier.
It is used based on the judgment that organic polymer films are insulating. Therefore, its I'7 can only be used as an extremely thin film with a thickness of about 5) tm at most, and carriers must pass through the film due to the tunnel effect, or when the l-tunnel effect cannot be expected ('), the practical residual potential is It is only used in thin films that do not pose a problem.

While examining the application of organic polymer films to a-' S 1 photoreceptors, the present inventors found that organic polymer films, which were originally thought to be insulating, exhibit electrical resistance when they reach a certain hydrogen content. It was found that the charge transport properties began to decrease.

Furthermore, an intermediate layer with hydrogen-containing carbon rise and polarity adjustment is provided on the conductive substrate. I found out that it gets 1 defense.

The present invention further improves the adhesion between the photoconductive layer and the substrate by using two continuous hydrogen-containing carbon films as an intermediate layer between the substrate of the photoreceptor and the photoconductive layer, and also reduces charge from the substrate. The purpose is to improve the sensitivity of the photoreceptor by suppressing the injection of ion and reducing the residual potential.

A means for solving the problem, that is, the present invention, consists of laminating an intermediate layer (2) mainly composed of a carbon film on a conductive substrate (1), and a photoconductive layer (3) on top of the intermediate layer (2). Relating to a photoconductor characterized in that the carbon film constituting the intermediate layer contains hydrogen in an amount of 0.1 to 67 atomic% based on the total atomic weight, and contains an element of group IA or VA of the periodic table. .

The photoreceptor of the present invention is composed of at least a photoconductive layer and an undercoat layer, which is an intermediate layer formed between the photoconductive layer and the substrate. - has a layer (denoted as T),
The polarity of this layer is adjusted by the TIIA group or the At1A element.

The photoconductive layer is not particularly limited, and may be made of amorphous silicon (a-81) (to change the characteristics, various elements such as C, OlS, N, P, r(, H(1), Ge, etc.) may be used. May contain multi-layered manoko t'fA
L), Se, 5e-1'c, CdS, copper phthalonoanine, inorganic substances such as zinc oxide, hisazo pigments, triarylmethane dyes, thiazine dyes,
Oxazine dyes, gizanthene dyes, soanine dyes, styryl dyes, pyriliuno dyes, azo pigments, quinacridone types, ingo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments Indus [1116] Organic substances such as J-based pigments, squarylium-based pigments, and phthalon-anine-based pigments are used with binder resin.
It may be 80 years old.

In addition to this, any material that absorbs light and generates charge carriers with extremely high efficiency can be used, even if it is a raw material.

The hydrogen content in the C:T-T undercoat layer preferred for the present invention is 1 to 67 atomic% (hereinafter referred to as atm
%), but to further improve adhesion and improve strain resistance by -1, hydrogen-containing fil I#: 40-67a
tm%, preferably 45 to 65 atm, %, particularly preferably 4 (1 to 60 atm, %). The hydrogen content and structure in the C:H undercoat layer can be determined by elemental analysis, infrared absorption spectroscopy, 'H-NMR. Or lec NM
It can be quantified by R etc. Hydrogen may be partially replaced with halogen, such as chlorine or bromine.

Such a membrane has improved water repellency and abrasion resistance. For normal electrophotography, the grindness of the C:H undercoat layer is 0.01.
~5 μm, especially 0.05 to 1 μm is suitable, and 0.0
If it is thinner than 1 μm, the adhesion between the photoconductive layer and the substrate will not be improved, and the effect of suppressing charge injection from the substrate will be small. 5μm
If it is thicker, it is not preferable in terms of productivity.

Invention C: The H undercoat layer is formed by a method such as ionization vapor deposition, ion beam vapor deposition, direct current,
It may be formed by a method of forming through a plasma state such as a high frequency or microwave plasma method, a method of forming from neutral particles such as a CVD method, a vacuum evaporation method, a sputtering method, or a combination thereof. However, for example, when the photoconductive layer is formed by the high frequency plasma CVD method, it is preferable to form the undercoat layer by the same method, as this leads to labor savings in the manufacturing process.

C: As a carbon source for forming the I-I undercoat layer, C2T (2, C7■ to I8, C2I-■4,
C31T, l, CH,, C4H, o, C4H6, C4I
-I,,C3H8,0.

Examples include H,, CH3CCH, and the like.

L; J: f-T, Ar, Nc, H as carrier gas
A etc. are appropriate.

In the present invention, an IllΔ group or VA group element is mixed in order to adjust the rectifying properties of the above C:IT undercoat layer.

That is, in the present invention, C is formed between the substrate and the photoconductive layer.
:H undercoat layer (2) is 11A when charged.
By containing a group element, it becomes P type, and when charged, it becomes VA type.
It is adjusted to N type by containing group elements. As a result, the negative charge induced in the substrate during ten-band processing is reduced to C:I-
Since the 1 under 1 coat layer itself is adjusted to P type,
The injection is blocked, and the movement of holes generated in the photoconductive layer to the substrate is facilitated. Similarly, during single-band processing, it becomes easier to prevent injection of positive charge and move electrons to the substrate, resulting in improvements in charging, dark decay, and sensitivity. In addition, in connection with this, when the photoconductive layer itself is used as a surface layer, the surface side is N
It is effective to prevent the injection of surface charges if it is adjusted to be P type when charged.

In other words, when the photoreceptor is used with ten charges, the substrate side is relatively P type and the front side is N type, and when it is used with negative charges, the substrate side is relatively N type and the front side is P type. By doing so, a reverse bias effect is produced. This achieves effects such as improved charging ability, reduced dark decay, and improved sensitivity.

Such pole-side tuning may be achieved by gradually increasing the content of HA or VA elements in a single layer toward the substrate or surface, or by adding a uniform concentration of IA to the surface.
A single C:H undercoat layer containing Group or VA elements may be provided on the substrate side. Furthermore, if necessary, a plurality of c:rr films having different concentrations may be provided so that a depletion layer is formed in the junction region.

1 to 6 are schematic cross-sectional views showing one embodiment of the photoreceptor of the present invention. The photoreceptor of the present invention is formed by laminating an intermediate layer mainly composed of a carbon film on a conductive substrate, and a photoconductive layer on the intermediate layer. The photoconductive layer may be a single layer or a stack of a charge generation layer and a charge transport layer. Furthermore, a laminate of many materials having different light absorption characteristics and electrical conductivity may be used. A surface protective layer may be provided on the photoconductive layer.

The photoreceptor shown in FIG.
・■] This is an example in which a photoconductive layer (3) with a thickness of 5 to 50 μm, which serves both as charge retention and transport, is laminated on the undercoat layer (2), and the peeling resistance from the substrate (1) is significantly improved. At the same time, prevention of charge injection from the substrate and light guide +3H
，-? The injection of the charge gear to the substrate, which occurs at i, is guaranteed.

Figure 2 shows an example in which the C:H film (2) used as the undercoat layer is also used as the surface protective layer (6) in the photoreceptor shown in Figure 1. The direction of the surface potential is 2.

In addition, the thickness of the surface protective layer is preferably 0.1 to 5 μπ.

Figure 3 shows a photoreceptor with a functionally separated structure.
Plate (1), second C:H undercoat layer (2), thickness 01 to 571 m charge generation layer (4) and thickness 5 to 5
It is formed by sequentially stacking charge transport layers (5) of 0 μm. As the charge transport layer (5), the same material as in (2) can be used, for example, in In color.

FIG. 4 shows the photoreceptor shown in FIG. 3 further provided with a surface protective layer (6).

Figure 5 shows a photoreceptor with a functionally separated structure, and the substrate (
1) 10C.■] An undercoat layer (2), a charge transport layer (5), and a charge generation layer (4) are sequentially laminated.

Further, FIG. 6 shows the photoreceptor shown in FIG. 5 further provided with a surface protective layer (6).

When the photoreceptors shown in FIGS. 3 to 6 are used by imagewise exposure after the surface is positively charged with a corona charger, etc., the photoreceptors shown in FIGS. 3 and 4 have a charge generation layer. (4) Charge-generated electrons are on the upper charge transport layer (5)
In the photoreceptor shown in Figures 5 and 6, holes generated in the charge generation layer (4) conduct electricity in the charge transport layer (5). toward the sexual substrate (1) (J
On the other hand, after negatively charging the surface of the photoreceptor, the electrostatic latent image is formed with suitable brightness attenuation.
When using ij image exposure, the behavior of electrons and holes can be exchanged to understand the running performance of the gear.

In FIGS. 3 and 4, 1 (i) for image exposure is ?
Although it passes through the 1H1ir transport layer (5), since the charge transport layer according to the present invention has excellent light transmittance, it is possible to form a suitable latent image.

In any type of photoreceptor, as described in 1-1, CII
The undercoat layer (2) contains a 111Δ group element during processing and a group ■Δ group element during - charging, which prevents charge injection from the substrate and also serves as an undercoat layer. The I layer itself has a charge transport function and is a photoconductive layer (
The charge galley generated in 3) should be sent out to the board side without being trapped.

The lnA group elements used are I3, ΔQSGa11
In order to mix Group 1 nA elements, of which B is particularly bright, into the C:H undercoat layer, an appropriate gaseous compound containing these elements is ionized together with a hydrocarbon gas. The film may be formed in a plasma state or a plasma state. Alternatively, the formed undercoat layer may be doped by exposing it to a compound residue containing an HA group element.

B-containing compounds that can be used in the present invention include T3(O
Ct T-15) 3, B2I-L, BCf13, BB
Examples include r3, B P 3, and the like.

Compounds containing eight are A j2. (o 1-C3H
J3, (CH3)3A! , (C2H5)3A j2. −
(i-C4HII)3Ai, , AlCf1°, etc. are exemplified.

As a compound containing Ga, Ga (Oi-C3I-I 7
)3, (CH3)3Ga, (C2H5)3Ga5Ga(
43, GaBr3, etc.

As a compound containing In, In(O1-C3H7)3
, (CJLj3rn, etc.).

■The content of Δ group elements is 20,000 pp per carbon atom.
m or less, more preferably 3 to looOppm.

VA group elements used for polarity adjustment include P1Δs,
Although Sb is included, P is particularly preferred. This ■A group element is also I
[Can be introduced into the C:H undercoat layer in the same way as group IA elements.

Compounds containing group VA elements that can be used in the present invention include the following.

As a compound containing P, P O(OCl-T*:L+,
(02H5) As a compound containing 3P, PH3, PO(4, etc., ΔS), As H3, AsC, 93, Δ513r
a, etc., S1] as a compound containing 5b (OC7■-■5
)3.5bc42.5bHt, etc. are exemplified.

The amount of VA group elements introduced is 20,000 pp per carbon atom.
m or less, more preferably about 1 to IO00 ppm.

Further, other elements may be introduced into the undercoat layer of the photoreceptor of the present invention to adjust its properties.

The photoreceptors shown in FIGS. 1 and 3 may each be provided with a surface coating layer, an intermediate layer, etc. using different +A materials.

It is also possible to adjust the pan IS cap by adding 5iSGe to the photoconductive layer to reduce the interface barrier with the photoconductive layer. In Figure 1, there are many! ? t (>10 atm%)
By unevenly distributing the Ge-doped portion on the Jl (body side) of the photoconductive layer, it is possible to prevent the reflection of excess light and prevent the occurrence of interference fringes, blurring, etc.

Examples of the Sl source include 5IH4; examples of the Ge source include GeH-.

The C:H undercoat layer of the photoreceptor of the present invention may further contain nitrogen, oxygen, sulfur and/or various metals, or a portion of hydrogen may be replaced with halogen.

Generally, nitrogen is N2, NH3, N20, No.

C,85N H2,I(CN,(CH,)3NSCH3
NH2, NO7, etc. are used, and by mixing them, the interface barrier with the photoconductive layer can be reduced.

As an oxygen source, 02.03, N20SNo.

Examples include C01C2H40, Cot, CH30CH3, etc., and by mixing this, the charging ability is improved.

As a sulfur source, CS 2, (C2H5) 2 S SH
2S.

Examples include SF6 and SO7. Mixing sulfur is particularly effective in preventing light absorption and interference in amorphous carbon.

Examples of metals that can be mixed include the following (the following are examples of gases that can be used for mixing).

Ba: Ba(OC2H3)3: Ca: Ca(O
c, +r5):+;Fe: Fe(Oi-C3T(7)
3, (C2H5), PC.

Fe(Co)5; Ge: Ge(OC, H,,
)4, (C3T-+5)4. Ge, GeCQt, G
eT-T,;Hf・Hf(Of-C3I(7): K
: KOi-C1,N7; Li: LiO1-Ge
N7: La: La(O1-CJL+)4; Mg:
Mg(OG H5)2, (C, I-T,)7Mg.

Na: Na04-C3H7; Nb: Nb(OC
plL)s:Sr: 5r(OCH3); Ti:
Ti(Oi C:+L17)4, Ti(OCd(e
) TiCρ4; Ta: Ta(OCzH5)5: V: VO(QC
7116) 0, VO(OtC-H-)3; Y:
Y (0+-C3T-L,)l;Z n: Z n(
OC2H5)2, CCT-1, ), 7. n.

(c2n5), zn: Zr: Zr(Oi C, 1
T17)<;S n: (CN3)4S n, (C2l
-+5) 4S nXS nCL; Cd: (CN3),
Cd; Co: C02(GO)n:Cr: Cr
(Co)e; Mn: Mn, (co)1o; Mo:
Mo(CO)6, MoFe, MoCf2e; W: W
(Co)e, WF', SWCσe: Te: H2
Te; Se: H, Se0 Also, by replacing a portion of hydrogen with halogen, water repellency, abrasion resistance, and translucency are improved.
cpt, -CF3, etc. are formed, an antireflection effect appears, and n becomes small (1.39).

As carbon and halogen source, Ct H5Cfllc
, r-r3c, C, cr-r3cl, CH3Br, co
c, M,, CCfl 2 F 2, CH (4F2, CF
4, NO4, C.

Examples include F9.

The photoreceptor of the present invention has at least a photoconductive layer and an undercoat layer. Therefore, at least two steps are required to manufacture this. For example, when an a-Si layer formed using a glow discharge decomposition apparatus is used as the photoconductive layer, plasma polymerization can be performed using the same vacuum apparatus.

FIGS. 7 and 8 show a capacitively coupled plasma CVD apparatus which is a photoreceptor manufacturing apparatus according to the present invention.

FIG. 7 shows a parallel plate type plasma CVD apparatus, and FIG. 8 shows a cylindrical type plasma CVD apparatus. Both devices (J, in FIG. 7, electrode plates (22), (25), ]; and substrate (2)
4) is a flat plate type, and in Fig. 8 (J electrode plate (3)
0) and the substrate (31) are cylindrical in shape. Further, in the present invention, it can also be produced using a separate inductively coupled plasma CVD apparatus. The method for manufacturing the photoreceptor of the present invention is carried out using a parallel plate plasma CVD apparatus (
This will be explained using FIG. 7) as an example.

In the figure, (6) to (10) are respectively C7H,,IT,,B
2Hn 1SiI-+4, N20 gas is sealed in the first to fifth tanks, and each tank is connected to the first to fifth dedicated valves (11) to (15) and the mass flow controller (1
6) to (20). These gases are sent into the reaction chamber (23) via the main pipe (21).

A high frequency signal is supplied to the reaction chamber (23) via a capacitor. li
A flat earth electrode plate (25) is electrically grounded with the flat electrode plate (22) connected to j;;t (26) and on which a conductive flat substrate (24) such as AJj is placed
) are provided facing each other. In addition, the flat electrode plate (22) is connected to the DC voltage source (2) via the coil (27).
8), and in addition to the power applied from the high frequency power source (26), a DC bias voltage is additionally applied. Further, the conductive substrate (24) fJ placed on the electrode plate (25) is heated to, for example, room temperature to 350° C. by a heating means (not shown).

In the above configuration, for example, when manufacturing the photoreceptor shown in FIG.
L gas, 11 as a carrier gas from the second tank (7)
．． Gas, B 2 H and gas should be supplied from the third tank (8). On the other hand, from the high frequency power source (26), the flat electrode plate (2
2), apply a power of 30 watts-1kw, and if necessary, apply a voltage of 50V to
A DC bias voltage of 2 KV is applied to generate plasma discharge between both electrode plates, and a C:H undercoat layer (2) with a thickness of 0.01 to 5 μm is formed on the preheated substrate (24) i-.
form. This C.)-T undercoat layer contains 1 to 67 atm% of hydrogen in addition to B, but this hydrogen content varies depending on the type of starting material gas, the material gas and the right-hand gas (IT2).
, inert gas) ratio, discharge power, pressure, substrate temperature, DC
Depends on manufacturing conditions such as bias voltage, annealing temperature, discharge frequency, etc. 50V to I
Can be controlled by applying a bias voltage of KV3
By increasing the bias voltage, the hydrogen content can be decreased by increasing the bias voltage, and the hardness of the IT film itself can be increased. 2nd and 4th
Tanks (7) and (9)j: Formed as a layer based on a-8i by introducing IT3 and SiH4 gases. .

The present invention will be explained below with reference to Examples.

Example 1 (■) (Formation of intermediate layer) In the glow discharge decomposition apparatus shown in FIG.
:degree, 11. After creating a vacuum, open the first and second regulating valves (
11), (12) and (13) are opened, C and IL waste are output from the first tank (6), H and gas are output from the second tank (7), and B 2 H is output from the third tank (8). Mass flow controller (1) with pressure gauge 1Kg/cm2
6), (17) and (18) 1-! -ta.

Then, adjust the scale of each mass flow controller L-t:+A to set the flow rate of C, )-I4 to 50 sccm.

B 2 T-1o + H? 150sccmSBtI
Io/C7Ht was set to 30 ppm and flowed into the reaction chamber (23). After each flow rate became stable, the internal pressure of the reaction chamber (23) was adjusted to 0.3 Torr. On the other hand, as the conductive substrate (24), 3X
A 50 x 50 mm aluminum plate was preheated to 250°C, and when the flow rate of each gas was stabilized and the internal pressure was stable, the high frequency power source (26) was turned on and the electrode plate (22) was heated to 1. Power of OOwatts (frequency 13, 56 Ml
-1z) and a DC bias of -1700 volts to perform plasma polymerization for about 1 hour, and conductive substrate (24)
A C:I-J undercoat layer (intermediate layer) containing about 45 aim % hydrogen and having a thickness of about 10 μm was formed thereon.

(IT) In the glow discharge decomposition apparatus shown in FIG.
and open the second regulating valves (11) and (12), and release C, I (4 gases) from the first tank (6) and the second tank (7).
From IT, gas was allowed to flow into the mass flow controllers (16), 1 and (17) under an output pressure gauge IKg 7 cm2. 2. Then, adjust the scale of each mass flow controller to adjust the flow rate of C, 1, -1 to 60scc.
m, H3 was set at 40 sccm and flowed into the reaction chamber (23). After a while, each flow stabilized...
The internal pressure of the reaction chamber (23) was set to 0 Torr; J7.1'11%. On the other hand, a conductive flat substrate (
24) As for (j, 3 x 50 x 50 mm aluminum plate, preheated to 250 °C, each gas flow ji1 stabilized, internal pressure stabilized, high frequency power supply (2
6) into the flat electrode plate (22) for 200 waits.
Plasma polymerization was performed for about 7 hours by applying s'ri force (frequency 13, 56 Ml(z)), and the conductive flat substrate (24)-1- was coated with IT to a thickness of about + containing about 56 atm%.
A C:II electron A:i transport layer of 07zm was formed.

The application of power from the high frequency source (26) was temporarily stopped to create a vacuum inside the reaction chamber.

The fourth and second regulating valves (i4) and (12) are opened, and the SiH4 gas is released from the fourth tank (9) and the second tank (
7) From T-I, gas output pressure gauge IKg/cm'
Mass flow controllers (19) and (17) under
It flowed inside. Adjust the scale of each mass flow controller to set the flow rate of 5il-I4 to 90 sccm, B2H
e, the flow rate of H7 is 210 sccm, B2He/S
iH+ was set at 20 ppm and allowed to flow into the reaction chamber. After each flow rate stabilizes, the internal pressure of the reaction chamber (23) reaches 1.
It was adjusted to 0 Torr.

When the gas flow H1 is stable and the internal pressure is stable, turn on the high frequency source (
26) and applied IOW power (frequency 13, 56 MT-1z) to the flat electrode plate (22) to generate glow discharge. This glow discharge was performed for 40 minutes to form a 171 m thick a-8i:H charge generation layer.

The obtained photoreceptor has an initial surface potential (V o ) −+ 60
7 half-reduced exposure m E r / 2 of 0 vol is 2
, 7 ffux-see. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

The following results are summarized in Table 1. Table 1 also shows the results of evaluating the repeated stability of the photoreceptor. "Peelability" indicates the adhesion between the substrate and the adhesive layer, ○ indicates that there was no peeling property, △ indicates that the edge was peeled off, and × indicates that it was completely peeled off. . In the evaluation of repeated stability, ○ (J is very good, △ is good, and × is unusable).

-27 = =28 - Examples 2 to 24 According to Example 1, an intermediate layer, a charge transport layer, and a charge generation layer were formed on an AQ substrate under the conditions shown in Tables 2 to 24.

In Example 14, the charge generation layer was formed as described below.

Parts by weight Styrene 200 Methyl methacrylate 160 n-butyl acrylate 75 β-hydroxypropyl acrylate)・55 Maleic acid
8 Benzoyl peroxide
75 Ethylene glycol monomethyl ether 1.50 A mixture of the above composition was added dropwise to a reaction vessel containing 350 parts by weight of xylene and maintained at 105°C over 2 hours with stirring in a nitrogen stream to react. , 2 hours after the start of polymerization, 0.5 benzoyl peroxide was added.
Parts by weight were added and reacted for 8 hours while heating and stirring to obtain a hydroxyl group-containing thermosetting acrylic resin with a nonvolatile content of 50% and a viscosity of 800 cps.

34 parts by weight of this thermosetting acrylic resin containing hytroquine group and 6 parts by weight of melamine resin (Super Beckamine J 820, manufactured by Dainippon Ingi Co., Ltd.) were used as a binder, and these and 2.4.5.7- 20 parts by weight of titranitrosyanine (manufactured by Toyo Ink Co., Ltd.), 40 parts by weight of cellosolve acetate, and 10 parts by weight of methyl ethyl ketone were placed in a whole mill bottle and kneaded for 30 hours to prepare a photoconductive paint,
This paint has C:T (charge transport layer (charge transport layer)) shown in Table-14.
After coating and drying, an electrophotographic photoreceptor having a photoconductive layer of 1 μm thick was obtained.

Table-2 (Example 2) 1) Table-1 and same color table-3 (Example 3) Table-4 (Example 4) Table-5 (Example 5) Table-6 (Example 6) Table- 7 (Example 7) Table-9 (Example 9) Table-10 (Example 10) Table-12 (Example 12) Table-13 (Example 13) Table-14 (Example 14) Table-15 ( Example 15) Table-17 (Example 17) Table-18 (Example 18) =47- Table-19 (Example 19) Table-20 (Example 20) Table-21 (Example 21) Table-22 (Example 22) Table-23 (Example 23) Table-24 (Example 24) Ratio! ≦(佼-↓-で=----i1 According to Example I, A under the conditions shown in Tables 25 to 28
An intermediate layer, a charge transport layer, and a charge generation layer were formed on the Q substrate-H.

Table-25 (Comparative Example 1) Table-26 (Comparative Example 2) Table-27 (Comparative Example 3) Table-28 (Comparative Example 4) Abbreviation table -
An a-3iH layer having a film thickness of 5 μm was formed under the conditions shown in No. 29 to obtain an a-8i:I (photoreceptor).

The results are shown in Table-29.

Table 29 (Comparative Example 5) Comparative Example 6 On the intermediate layer produced under the conditions shown in Table 30, a polyethylene film was produced by a conventional method of organic polymerization, and then the
An a-8i:H layer having a film thickness of 17t7I was formed under the conditions shown in No. 30. Although the charging ability was the same as in Example 1, the sensitivity was only a slight potential attenuation due to the a-Si layer and did not reach the half value. The results are also shown in Table 30.

Table 30 (Comparative Example 6) Comparative Example 7 A carbon film containing no hydrogen was formed in the intermediate layer -1- produced under the conditions shown in Table 31 using the arc discharge deposition apparatus shown in FIG. In Fig. 7, inside the vacuum container (40) there is a power supply (41) connected to a power source (41).
carbon electrodes (43) and (4) are provided, respectively.
4) on the substrate holding stand (45) where ΔQ j
1 (Plate (46) is placed, and the pressure inside the container is
orr, the current applied to the carbon electrode was set to 50 A to generate an arc group 7u, and a thin carbon film containing hydrogen and having a thickness of 57zr1 was created on the Aρ substrate.

The obtained carbon film had a resistance of only 10 8 Ω·am or less, and could not be used as an electrophotographic photoreceptor.

In addition, under the conditions shown in Table 31, a-8i.
T (When the layers were laminated, film peeling occurred.

Table 31, (Comparative Example 7) Effects of the invention By using a polarized hydrogen-containing carbon film as the undercoat layer of the photoreceptor, charge injection from the substrate can be prevented, residual potential is reduced, and sensitivity is improved. can be achieved. Further, by introducing a group IIIA or group VA element, the adhesion of the carbon film is improved. Therefore, the excellent woody adhesion of the carbon film is made more effective. Also, board A
Q can be prevented from diffusing into the photoconductive layer.

[Brief explanation of drawings]

1 to 6 do not show schematic cross-sectional views of the photoreceptor of the present invention. 7 to 9 are views showing an example of an apparatus for manufacturing a photoreceptor according to the present invention, and FIG. 10 is a view showing the configuration of an arc discharge deposition apparatus used for comparison. The symbols in the figure are as follows. (1)...Substrate (2)...C:H undercoat layer (3)・Photoconductive layer (4)...Surface protection layer (5)・
・Charge transport layer (6) to (10) tank (11) to (
15)...Control valves (16) to (20)...Mass flow controller (
21)・Main pipe (22)...Flat type electrode plate (
23)...Reaction chamber (24)...Flat plate type substrate (25)...Flat type earth electrode plate (26)...High frequency power supply (27)...Coil (
28)・DC voltage source (29)・Vacuum pump (30
) Cylindrical electrode plate (31)... Cylindrical substrate (32)
・Thermostatic chamber (33)... Monomer (34)...
・Connecting pipe (40)...Vacuum container (41)...
Power source (42)... Electrode support rod (43), (
44) Carbon electrode (45) Substrate holding stand (46)
...AQ split board 67- Fig. 1 Fig. 2 Fig. 3; N4'A Fig. 5 Fig. 6

Claims (1)

[Claims] 1. Intermediate layer (2) mainly composed of carbon film on conductive substrate (1)
), and a photoconductive layer (3) is laminated thereon, and the carbon film constituting the intermediate layer contains hydrogen in a proportion of 0.1 to 0.1 to
A photoreceptor characterized in that it contains 67 atomic% of a Group IIIA or Group VA element of the periodic table.