JPS62238572A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a function separating type photosensitive body constituted of a charge generating layer and a charge transfer layer having superior charge transfer capacity, chargeability, and sufficient surface potential even in the case of thin film thickness by forming the charge transfer layer of a specified amorphous carbon film contg. H. CONSTITUTION:A function separating type photosensitive body constituted of a charge generating layer 3 and a charge transfer layer 2 is obtd. by forming the charge transfer layer 2 of amorphous C layer contg. H wherein the ratio (N1:N2) between the number (N1) of C atoms bonded to H and the number (N2) of C atoms not bonded to H among C atoms having unsatd. bond in its chemical structure is regulated to 1:4-1:0.2. When the a-C film is formed as the charge transfer layer 2 and the value of N2 is 4-0.2, more pref. 2-0.5, most pref. 1.25-0.88 setting the value of N1 at 1, it is suitable as charge transfer layer. The a-C film having the value of N1:N2 within this range has >=10<11>OMEGAcm specific resistance and the mobility of carrier >=10<-7>cm<2>/(v.sec), providing thus sufficient charge transfer function.

Description

[Detailed description of the invention]

Field of Application of Industry-1 The present invention relates to photoreceptors, particularly electrophotographic photoreceptors. BACKGROUND ART In recent years, amorphous silicon (hereinafter referred to as a-Si), which is manufactured by plasma chemical vapor deposition (hereinafter referred to as I)-CVD method, has been used for photoreceptors, particularly electrophotographic photoreceptors.
) has been adopted. The a-S i photoreceptor has various excellent properties. However, a-Si has a large dielectric constant ε of about 12, so there is a problem in that a film thickness of at least about 25 μm is essentially required in order to obtain a sufficient surface potential as a photoreceptor. The a-S i photoreceptor requires a long time to manufacture due to the slow deposition rate of the film in l)-CVD method, and the longer the manufacturing time to obtain a homogeneous film of a-S: It becomes difficult. As a result, the a-Si 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 drawbacks, it is essentially not desirable to make the film thinner than this. On the other hand, the a-Si photoreceptor has drawbacks such as poor adhesion between the substrate and the a-Si, as well as poor corona resistance, environmental resistance, and chemical resistance. In order to solve such problems, it has been proposed to provide an organic plasma polymerized film as an overcoat layer or an undercoat layer of the a-9i photoreceptor. Examples of +"rri are known, for example, in JP-A-61761, JP-A-59-214859, JP-A-51-46130, and JP-A-50-20728. , the latter example is disclosed in Japanese Patent Application Laid-Open No. 60-433541, for example.
No. 59-136742, JP-A-59-136742, JP-A-59-136742
-2.8161 publication or JP-A-59-38753
No. 2, etc. are known. Other examples using the plasma polymerization method include JP-A-59-148326 and JP-A-56-6044.
No. 7 or Japanese Unexamined Patent Publication No. 120527/1983 are known. Organic plasma polymerized films can be prepared from all kinds of organic compound gases such as ethylene gas, benzene, and aromatic compounds (e.g., Ni, Ti, Bell (Δ, 'l', I'
3ell), M., Dien (M., 5hcn) et al., Journal of Applied Polymer Science (.
IounalorApplied Polymer
5science), Volume 17, pp. 885-892 (1
973), etc.), but organic plasma polymerized films produced by conventional methods are used only for applications that require insulation. Therefore, these membranes have an electrical resistance of about <10” Ωam like ordinary polyethylene membranes (T・
Once a month, I used an insulating film, or at least one that was recognized as such a film. JP-A-Sho (io-617 (i1 publication), the technology cited is 5
This disclosure discloses a photoreceptor coated with a diamond-like carbon insulating film having a thickness of 0.00 to 2 μm as a surface protective layer. This carbon thin film is intended to improve the corona discharge resistance and mechanical strength of the a-Si photoreceptor. The polymer membrane is very thin, and charges move through the membrane through the tunnel effect, so the membrane itself does not require charge transport ability. In addition, there is no mention of the carrier transport properties of 1-unit plasma polymerization, and there is no way to solve the above-mentioned wood quality problem of a-3i. How many transparent film overcoat layers with a thickness of about 5 μm have been disclosed that are coated with organic hydrocarbon monomers such as or acetylene by plasma polymerization? It improves durability, pinholes, and production efficiency by 1 to 1.There is no mention of the gear transport properties of the organic plasma polymerized film, and it solves the above-mentioned essential problems of A-3i. - It is not a filth. Japanese Patent Application Laid-Open No. 51-4G130 discloses that N-vinylcarbazole is applied to the surface by glow discharge to
A photoreceptor formed as a 1 μm organic plasma polymerized film is disclosed. The purpose of this technology is to make it possible to use poly-N-vinylcarbazole photoreceptors, which could only be used with positive charging, with bipolar charging.
It is very thin with an O1-3μ image and can be used as an overcoat. It is thought that polymerization +1i is very thin and does not require electron 6:i transport ability. Manoko, there is no mention of the carrier transport properties of polymeric membranes, and the 1 possessed by a-S i.
1; It does not solve the essential problem mentioned in i. JP-A No. 50-20728 discloses that a sensitizing layer and a photoconductive electrical insulator are sequentially laminated on a plate, and then a glow layer with a thickness of 0.1 to 1 μm is applied to the plate. A technique for forming a discharge-polymerized film has been disclosed, but this film has the ability to withstand the 7.J-type phenomenon and protect people in public.
Use it as an overcoat. The polymer membrane is very thin and is not used as a cargo transport layer. Regarding the carrier transport properties of polymer membranes -
・There is no cut-off description, and there is no way to solve the essential problem described in 1lii of a-Si. Japanese Unexamined Patent Application Publication No. 3541 discloses that diamond-like (200 to 2 μm) diamond-like (
A photoreceptor using an R-machine plasma polymerized film is disclosed, but the T-machine plasma polymerized film improves the adhesion between the substrate and the a-Si, which is the objective. ν is good, ?u (!Nia moves in the film due to the tunnel effect, and the ?tt ?Nia movement itself does not require ?Nia transport ability. Also, there is no mention of the carrier transport properties of organic plasma polymerized films. Kanashi, a-3
It is not possible to solve the wooden problem described in i. Japanese Unexamined Patent Publication No. 1983-13 (I742) discloses a semiconductor device in which a FR plasma polymerized film and a silicon film of approximately 57 tm are sequentially formed on a substrate. However, the FR plasma polymerized film is , a of the aluminum substrate
- Preventing diffusion into Si], but there is no mention of the manufacturing method, film quality, etc. Furthermore, there is no description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and there is no way to solve the essential problems of a-9i. JP-A No. 59-28161 discloses a photoreceptor in which a (1) machine plasma polymerized film and a-9i are sequentially formed on a substrate. It is an undercoat layer that utilizes the same properties as a pro-lagging layer, a tangent layer, or an anti-peeling layer.The polymer film can be very thin (5 μm, preferably 1 μm or less). <'A? Transport ability does not cause the problem of -η1 of surface potential (residual potential).Repeated use increases the electric field in the undercoat, which increases carrier passage (tunneling). This is because there is a phenomenon in which the rise in residual potential is suppressed to a low level due to the effect of As for the carrier transportability, there is no difference in -kiri86, and the +'+ of a-S i
It does not solve the essential problem described in rf. Japanese Unexamined Patent Publication No. 59-38753 describes oxygen, nitrogen, 1-
by plasma polymerization from a mixed gas of hydrocarbons and hydrocarbons.
A technique is disclosed in which a thin model of 100 N-machine plasma panels is formed and an a-Si layer is formed on the thin model. Compared to other FF polymers, Shira's plasma polymerized film does not undergo thermal deterioration, and is an undercoat layer that utilizes insulating properties, so it functions as a blocking layer or anti-peeling layer. be. Polymerized membranes are very thin, and charges move through the membrane due to the channel effect; the membrane itself does not require the ability to transport charges. In addition, (there is no mention of the carrier transport properties of the f-machine plasma ILI composite film, and a-9i's point 1) "It does not solve the essential problem described in J. The publication is characterized in that the gas is pre-decomposed and pre-combined.I)-CVl) AV
Although a method for producing an i-film is disclosed, the embodiments only exemplify a method using a Si-based material. Japanese Patent Application Laid-open No. 56-60447 discloses a method of plasma polymerizing the vapor of a mixture of a halogen compound and a halogen compound to form an a-type conductive film. This technology is based on a plasma-polymerized membrane introduced with hydrogen in the near-infrared region (0.8 to 3.0 μm).
However, the film has been shown to have high sensitivity for use in near-infrared sensors, and as in the present application, it has been shown to have high sensitivity for use in electrophotographic photoreceptors. Furthermore, there is no mention of whether or not it can be used for photoreceptors. Japanese Unexamined Patent Publication No. 53-120527 discloses a method of forming a single layer of positive-type radiation-sensitive timber by a plasma-containing method using hydrocarbons and hydrogen halides. This case is a method of producing a positive-type dielectric material by crosslinking with electron beams, X-rays, λ rays, or α rays, and is not intended for use in electrophotographic photoreceptors. . As described above, the various composite films used in photoreceptors have been used as an undercoat layer or an overcoat layer, but they are not suitable for transporting carriers. It is a film that does not require any function, and is used based on the judgment that it is an organic IR polymer film with insulating properties. Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and if carriers pass through the film by tunneling effect, or if the l tunnel effect cannot be expected, it is problematic as a practical residual potential. It can only be used with a film as thin as 4" without becoming insulating. It was thought that carbon atoms (e.g., carbon-carbon double bonds, quaternary carbons, etc.) containing carbon atoms (e.g., carbon-carbon double bonds, quaternary carbons, etc.) ■When it becomes, electric low Ui etc. change,
It was discovered that at a certain percentage, it begins to show 7u cargo transportability.
It was. The present invention solves the problems of the conventional a-Si photoreceptor by taking advantage of the new findings.
We have solved all the problems of 5a-9i in terms of film thickness, manufacturing time, manufacturing cost, etc., and the purpose of use and characteristics are completely different from that of the conventional one.
[1] The purpose of the present invention is to provide a photoreceptor using a composite film and a method for manufacturing the same. Means for reducing the I decoy point to IFXi, that is, the present invention provides a function-separated photoreceptor having an electric 6:I generation layer (3) and an electric transport layer (2).
The transport layer (2) is an amorphous carbon film containing hydrogen, and among carbon having unsaturated bonds in its chemical structure, the ratio N of the number of carbons bonded to hydrogen N1 to the number of carbons N2 not bonded to hydrogen, The present invention relates to a photoreceptor characterized in that :N is l:4 to l:0.2. The photoreceptor of the present invention is composed of at least a charge generation layer and a charge transport layer. The charge transport layer is a hydrogen-containing amorphous carbon film (hereinafter referred to as
a-clIQ). The hydrogen content in the hydrogen-containing rT carbon film is 20 to 67 atomic%, preferably 4
0-G7 atomic%, especially 45-65 aLO
It is desirable that the content be fflic%. If the amount of hydrogen contained in the a-C film is less than 20 atomic%, suitable transport properties cannot be obtained, and if it is more than G 7 a[omic%, the film quality deteriorates and the film formability decreases. 0 The photoreceptor of the present invention is characterized by having an a-C layer as a charge transport layer.Furthermore, the carbon contained in the a-C film has an unsaturated bond that is bonded to hydrogen. The ratio of the number of carbon atoms N1 to the number of carbon atoms not bonded to hydrogen N2, N,:N, is l:
4 to 1:0.2. In the a-C film of the present invention, there are carbon atoms with various bonding modes, such as single bonds (free radicals (living radicals)), double bonds, triple bonds, etc., and these also have hydrogen atoms. If the carbon atoms in the a-C film of the present invention are carbon having an unsaturated bond and bonding to hydrogen, Infrared absorption spectra,

[Nuclear magnetism by 1 ton] ('II-NMIυ or nuclear magnetic resonance by 13C)
In the present invention, an unsaturated bond refers to a carbon-carbon double bond and/or a carbon-carbon triple bond. Among the carbons having bonds, the number N1 of carbons bonded to hydrogen and the number N1 of carbons not bonded to hydrogen,
It is important that the ratio N + :N t is between l:4 and l:o.2. The a-C film of the present invention has N, where the value of N is l. The value of is 4 to 02, more preferably 2 to 0.5, especially ■,
When the film is between 25 and 0.88, it is suitable as a charge transport layer, and when it is larger than 4, a photoreceptor using such a film as a transport layer has an increased charging ability but a decrease in photosensitivity. As a result, the photoreceptor characteristics deteriorate. If it is smaller than 0.2,
The charging ability of the photoreceptor decreases, resulting in almost no photosensitivity. N +: a-CIIQ with N x in this range is
The specific resistance is IQIIΩCM or more, and the carrier mobility is l
O”-7cm1/ (v-5t=c) or more,
Good 7t! You can get cargo transportation function. In the a-C film according to the present invention, there are various bonding modes of 1,
υbub: i r is 7? However, the number of suspensions, j and υ, can be determined from the composition analysis and specific gravity of the membrane. Zunawa 1''), the compositional analysis ratio of C and It of the a-C film is Cx1ly
(x+y=1) and the specific gravity of the film is W (g/cm'), then the total number of carbon atoms Cc in the film ICIIIJ is calculated by the following formula [1
]: In the L formula, Cc is the total number of carbon atoms, W is the specific gravity, X and y are the compositional analysis ratios of carbon and hydrogen, and 8 is the avocado
, '4/11101). ] You can obtain it according to the following. In the present invention, a film in which the number of carbons having unsaturated bonds is 5 to 50% of the total number of carbons is desirable. The thickness of the a-0 layer is suitably 5 to 50 .mu.m, particularly 7 to 30 .mu.m; if it is thinner than 5 .mu.m: 1) the electric power is low and it is not possible to obtain a sufficient density of the copied image. If it is thicker than 5oBm, it is not preferable in terms of productivity. This a-0 layer is translucent,
It has a high dark resistance and is rich in electron:f transport properties, and when the film thickness is set to 5 μm or more as described above, it transports the gear without generating 6 charge traps. The organic compound for forming the a-C layer does not necessarily have to be in a gas phase; it can be a liquid ((
It can be used either as l or solid phase. As the hydrocarbon, for example, methane series hydrocarbons, ethylene series hydrocarbons, acetylene series hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. may be used. Examples of methane series hydrocarbons include methane, ethane,
Propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, )・
Lyzocane, tetradecane, pentadecane, heptadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docozan, tricosane, tetradecane, pentagene, hegisacozane, hebutacozane, octadecane, nonacosane, triacozane, dotriaco→
Normal paraffins such as non, pentatria concune, isobutane, isopentane, neopentane,
Isohexane, neohegizan, 2,3-dimethylbutane, 2-methylarene, 3-ethylpentane, 2,2-tsumethylpentane, 2,4-tsumethylpentane, 3.3-
trimethylpentane, trizotane, 2-methylhebutane,
3-methylhebutane, 2,2-nomethylhexane, 2,
2.5-dimethylhexane, 2,2.3-1-methylpentane, 2,2.4-trimedelpentane, 2.3
．． Isoparaffins such as 3-trimethylpenkune, 2,3.4-1-trimethylpentane, isonanone, etc. are used. J, thidine series hydrocarbons include, for example, ethylene, propylene, isobutylene, 1-butene, 2-butene, 1
-Pentene, 2-pentene, 2-methyl-1-butene,
3-Methyl-'-butene, 2-methyl-2-butene, l
-hexene, tetramethylethylene, I-heptene, l
-Olefins such as octene, l-nonene, 1-decene, etc., diolefins such as allene, methylalene, butadiene, pentanoene, hexadiene, cyclopentadiene, etc., and triolefins such as ocimene, alloonemene, myrcene, hexatriene, etc. , etc. are used. Examples of acetylenic hydrocarbons include acetylene,
Methylacetylene, l-butene, 2-butene, 1-pentyne, ■-hexyne, 1-heptyne,! -octyne, 1
-nonine, l-decyne, etc. are used. Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopencune, cyclononane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, Schiff [
1 Hegizadecane, etc., cycloparaffins, and Schiff [
l Propene, cyclobutene, nku [l pentene, nku (
1 Olefin, 1 Hexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, etc.
12, limonene, terbirun, phelandrene, sylhestren, tsien, carene, pinene, bornidine,
Kung Huen, Huen Cheng, Ng [l] Kong Huen, Tricyclen, Pizzabojin, Jingibezin, Curcumen,
Terpenes such as fluorene, cadinense sesquibenhen, selinene, caryophyllene, zantadine, cedrene, camposin, phylloclatene, bodocarprene, midine, and steroids are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isobutylene, di:Idine, pentamethylbenzene, hegizamethylbenzene, ethylbenzene, but(1-pyrubenzene, cumene, sudizine, biphenyl, terphenyl, diphenylmethane, triphenylmethane, benzyl, stilbene, octene, naphthalene,
Tetralin, anthracene, phenanthrene, etc. are used. In the present invention, when a-CIli is formed, a bipedal compound is used in a mixture of two or more types of gases,
1) Yes. In the a-C film, many convex columns (polymers (block copolymers, brats, etc.) are formed, which improves hardness and adhesion properties.Alkane hydrocarbons (0
When using ITI using □It 2n + 2), it is possible to form a so-called i-C film, which is a diamond-like ultra-hard film with a hardness of Ij72QOO or more and an electrical resistance IGllQcm. However, the plasma conditions in this case require high temperature, low pressure, and high power, and it is also necessary to apply a DC bias of 4" to the plate. In the present invention, various plasma methods such as direct current, high frequency, low frequency, and microwave plasma methods can be used to form the a-C film.Alternatively, as described later, , ?1i magnetic waves (X-rays, laser beams, etc.) and bipedal plasma can be used in combination. By selecting these combination methods, the same monomer can be used to achieve various 5'4 characteristics (f For example, it is possible to obtain an i-C film with a low frequency plasma method (with a frequency of several
When using 11z to several hundred KI [about z], high hardness a-
Good Cl can be obtained. In the present invention, when forming an a-C film, it is important to consider the ratio N1:N2 of the number of carbon atoms bonded to hydrogen, viN, to the number of carbon atoms bonded to hydrogen, viN, among the unsaturated bonds (f). Tobenashi l: o, 2
It is to be formed so that. Also, 71'6:
When the r-generating layer is formed by high-frequency plasma or the I)-CV l) method, it is preferable to form the a-C film by the same method, as this leads to labor savings in the production process using one stroke of manufacturing equipment. The charge generation layer of the photoreceptor of the present invention is not particularly limited, and may be amorphous silicon (a-8i)! (Various different elements such as l11C, OSS, N, 13S to change the properties)
l'3. (may contain halogen, Ge, etc., and may have a multilayer structure), Sel'lX, 5c-As
film, 5e-TO film, CdS film, copper lid:,
, :/, Inorganic substances such as zinc oxide and/or bisazo pigments, triarylmethane dyes, deazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, azo pigments ,
Quinacridone pigments, in-novo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimigzole pigments,
Indathlon pigment, squarylium pigment, lid [1
Examples include resin films containing cyanine-based pigments, etc., which have a content of 1° organic substances.In addition, any material that absorbs light and generates electron carriers with extremely high efficiency may be used. It is a feed and can be used with a 4° filter. In the present invention, when the charge transport layer is formed by a plasma method, it is preferable to form the film by the same method as the charge generation layer, as this leads to reductions in manufacturing equipment cost and process labor. In addition, when the charge generation layer is provided by a known method, the surface of the powder of the above-mentioned material is treated in advance by plasma polymerization to form a thin film. For example, when dispersing these in a resin, use a k-side coat 4-rotate dispersion layer 1.2 to add rust and solvent resistance to prevent deterioration, etc. The electric generation layer can be placed anywhere on the photoreceptor, for example, it can be placed on the 2nd layer, the 13th layer, or the middle layer.
That's good. The film thickness depends on the type of material, especially its spectral absorption characteristics, the exposure light source, the exposure light source, etc., and is generally set so that absorption of 90 layers or more for 550 nm light can be obtained. In the case of a-9i, it is 0.1 to 3 μm. In the present invention, ac? T! In order to adjust the charging properties of the charge transport layer, hydrogen atoms other than carbon or hydrogen may be mixed. For example, in order to further improve the hole transport properties, surrounding 101 Table of Laws Group 111 Original r.
, or even if a halogen atom is mixed, kL). In order to further improve the electric transport properties, atoms of group 1 of the periodic table or alkali metal atoms may be mixed. In order to further improve the transport characteristics of both positive and negative carriers,
iSGe, alkaline earth metal, chalcogen 13'It
i' may be mixed. These atoms may have multiple JTIs, and depending on the purpose,
In the ad load transport layer, it is fine to mix only the specific (1γ(δ), or to adjust the concentration distribution, etc., but in any case, what is important is that unsaturated bonds are present in the plasma polymerized film. The ratio of the number of carbon atoms that is aJ-, the number of carbon atoms bonded to hydrogen, N, and the number of carbon atoms that are not bonded to hydrogen, N2 +: Nth'
1:4 to t:Q, 2. 1 to 12 are schematic sectional views showing one embodiment of the photoreceptor of the present invention. In the figure, (1) is J, (plate), (2) is a-CI as a charge transport layer, and (3) is Tli i!
The i generation layer is shown. In the photoreceptor of the embodiment shown in FIG. 1, for example, when it is charged ten times and then imagewise exposed, charge carriers are generated in the charge generation layer (3) and electrons neutralize the surface charges. On the other hand, holes are transported to the substrate (1) side guaranteed by the excellent charge (:j) transport properties of the a-C film (2). When the photoreceptor shown in Fig. 1 is used with one charge, Electrons are transported in a-CIIQ (2) in the opposite way to the above. , when electrons are used in the a-C film (2) at -.:1 electrons, holes are transported in the a-C film. Charge transport layer (2
) is set so that the charge-generating layer (3) is directly connected to the charge-transporting layer (2).1) - Photosensitive The body is 45 on the photoreceptor shown in FIGS.
, as layer (4) I! 1. A surface protective layer of 0.01 to 5 μm is provided (in the Jk example, when a photoreceptor is used, the surface protection layer is
and 71 depending on the environment! /i? Protection of generation layer (3) or charge transport layer a-C film (2) and direction of initial surface potential
1; The surface protective layer may be formed of any known material, and in the present invention, it is preferable to provide it by plasma polymerization from the viewpoint of production. Invention a-0 membranes may be used. This protective layer (4)
It is also easy to mix up heteroatoms. The 4" photoreceptor shown in FIGS. 7 to 9 is a photoreceptor shown in FIGS. In this example, depending on the substrate (1) used or its processing method, adhesiveness, t1', and human protection + lz effects are aimed at.For the undercoat layer, a known material may be used, and in this case as well. It is preferable that the film be formed by an organic plasma polymerization method.The a-C film according to the present invention may be used.Furthermore, an overcoat layer (4) shown in FIGS. 4-6 is provided on the photoreceptor shown in FIGS. (Fig. 10 to 1)
Figure 2). In the photoreceptor of the present invention, when the a-C film is on the outermost surface and has a hollow structure as shown in FIG. 2, FIG. 3, FIG. 8, or FIG. 9, oxygen, hydrogen, Inert gas or dry-edging gas (e.g. halogenated carbon),
Alternatively, it is possible to modify the surface by irradiating plasma of nitrogen or the like. By doing so, it is possible to further improve the moisture resistance, IT abrasion resistance, and charging ability of the photoreceptor. Does the photoreceptor of the present invention have a charge-generating layer? 1i4! j @ Farewell. Therefore, at least two steps are required to manufacture this. When using, for example, an a-9i layer formed using a GJ-discharge decomposition apparatus as the Tli d near generation layer, it is possible to perform plasma polymerization using the same vacuum apparatus, and therefore *CTli (:il
It is particularly preferred that the transport layer, surface protective layer, barrier layer, etc. be formed by plasma polymerization. The electron transport layer of the electrophotographic photoreceptor according to the present invention decomposes molecules in the gas phase by discharge under reduced pressure, and diffuses active neutral species or charged species contained in the generated plasma atmosphere to the substrate. , make it conductive by electric or magnetic force, and deposit it as a solid +11 by a recombination reaction on the substrate.
It is produced from a so-called plasma polymerization reaction. FIG. 13 shows an example of the photoreceptor manufacturing apparatus according to the present invention. 11! A plasma CV I) apparatus is shown below. Taking as an example a photoreceptor in which a plasma-polymerized polyethylene film is used as a cargo transport layer, the manufacturing method will be explained using FIG. 13. FIG. Related electrophotographic photoreceptor manufacturing apparatus 1
:'J: In the figure, (701) to (706) are always t1
1+! The original monomerized gas in the gas phase at time t is sealed in the first to i tanks, and each tank has the first to sixth ρ?+1 node valves (707) to (712) and the first to sixth flow rates. Controller (7 1 3) ~ (7 1 8
)It is connected to the. In the figure, (719) to (721) are the first J'r which encapsulates the raw material compound which is in liquid phase or solid state (11 states) at room temperature.
The temperature of each container can be controlled using the first to third temperature ovens (722) to (724) for vaporization, for example, room temperature to 150°C, or -50°C to room temperature. ,
Further, each container has seventh to ninth control valves (725) to (
727) and seventh to ninth stream m controllers (728) to (73
0). These gases are mixed in a mixer (731) and then sent into a reaction chamber (733) via a main pipe (732). The intermediate piping is heated by an appropriately placed piping heater (734) so that the gas obtained by vaporizing the raw material compound, which is in a liquid or solid phase at room temperature, does not condense on the way. has been done. Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (73).
G) are installed facing each other, and each electrode is connected to an electrode heater (7
37) by! Te fever is considered possible.゛,゛The U force applying electrode is equipped with a matching box for high frequency power (738
) via a high frequency power supply (739), a low frequency power supply (741) via a low frequency power matching box (740), a DC power supply (74: () or connected via a 1-pass filter (742)) The connection selection switch (744) allows the application of fri force with redundant frequencies.The pressure inside the reaction chamber rises to the pressure control valve (745) and is adjusted to the F
The pressure inside the reaction chamber is reduced using the exhaust system selection valve (74).
G), diffusion pump (747), oil rotary pump (
748), a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump. For IF gas, a further suitable exclusion device (753)
After making it safe and harmless, it should be exhausted into the atmosphere. These exhaust system pipes are heated by appropriately placed pipe heaters to prevent the vaporized gas from the raw material compound, which is in a liquid or solid state at room temperature, from condensing on the way.
It is said that heating is possible. For the same reason as the reaction chamber, heat can be supplied by the reaction chamber heater (751), and a conductive substrate (
752) is installed. In FIG. 13, the conductive substrate is fixed to the ground fit electrode, but it is fixed to the power application electrode and the conductive substrate is fixed to the ground fit electrode.
】; Furthermore, 6 may be placed on both sides. The reaction chamber used for photoconductor production is equipped with a diffusion pump and a glue stop.
The pressure is reduced to about 0'''4 to lO''''1, and the degree of vacuum is checked and the gas adsorbed inside the device is desorbed. At the same time, the electrode heater is used to heat the ?1i electrode and the conductive The temperature of the substrate is raised to a predetermined temperature by 4 degrees.Next, the raw material gases are transferred from the first to sixth tanks and the first to third containers to the first to ninth flows to the first controller. Introduce it into the reaction chamber while keeping the amount constant, and put it into the pressure regulating valve.)
; Maintain a constant reduced pressure inside the reaction chamber. After the gas flow rate is stabilized, the connection selection switch selects, for example, high frequency 7tt*i, and high frequency power is applied through the power application electrode. A discharge is started between the two electrodes, and a solid phase film is formed on the substrate within a certain period of time. (733) to a constant vacuum state, C!I1.
) to supply H gas as a carrier gas. On the other hand, the upper electrode plate (736) is connected to the high frequency power source (739).
to

[A power of OwaLLs-1jvaLLs is applied to generate plasma emission 7u between both electrode plates, and the preheated ΔQ
An a-C charge transport layer (2) with a thickness of 5 to 50 μm is formed on the substrate (752).This charge transport layer removes the unsaturated bonds in the a-〇 film produced according to the present invention by YT. The ratio of the number of carbon atoms bonded to hydrogen, N, and the number of carbon atoms not bonded to hydrogen, N+:NJ (1:4 to 1:0.2
It is. Although this ratio depends on other manufacturing conditions, it can be controlled by applying a bias voltage of IOV to IKV from the DC voltage source (743). That is, by increasing the bias voltage, the number of unsaturated bonds (-j-) bonded with hydrogen can be decreased by increasing the bias voltage, and the hardness of the a-C film itself can be increased. a-C
The transport layer has excellent light transmittance and dark resistance, and is highly effective in transporting charge carriers. Note that, for example, n, II, gas from the fourth tank (704) or I)113 gas from the fifth tank (705) is introduced into this layer to control it to a P1N type to further enhance charge transport properties. Also good. Next, the generation layer (3) generates I'lt, 5i11. from the second and third tanks (702) and (703).
It is formed as a layer containing a-S+ as a base material after introducing the gas. Also, md! When the compound to be introduced into the reaction tank (733) for forming the transport layer is a liquid substance, gas may be introduced into the reaction tank (733) by the method described above and plasma polymerized. In addition, when forming an a-C film from an organic compound with a high boiling point, the material is coated on the Jl (plate) in advance, and then plasma such as a carrier gas is irradiated in a vacuum chamber. In the present invention, the aC film forming plasma polymerization method further uses electromagnetic waves such as laser beams, ultraviolet rays, X-rays, or electron beams. The irradiation is carried out either by itself or with -11 auxiliary irradiation to form an a-C film (photo-assisted method), or by the assistance of a magnetic field or a bias DC electric field. 〇It is effective when you want to increase the deposition rate of the film, further shorten the manufacturing time, or when you want to increase the height of the a-C film.Hereinafter, examples will be explained. Example 1 Formation of charge transport layer (a-C layer) In the glow discharge decomposition apparatus shown in FIG. 13, first, the inside of the reaction vessel (733) was ' After creating a high vacuum of approximately Torr, open the first and second valves (707) and (708), and pump C7 from the first tank (701).
4 gas, 11. from the second tank (702). Gas was allowed to flow into the mass flow [I-controller (713) and (714)] under an output pressure gauge of 1 Kg/cm''.
Each mass [1- Adjust the scale of the controller, C,
II. The flow rate was set to be 30 sec, and I[t was set to be 65 sec, and the mixture flowed into the reaction tank (733). After each flow fit becomes stable, the internal pressure of the reaction tank (733) becomes 0.
, 5 Torr. On the other hand, as the conductive substrate (752), a 2x50x50 aluminum temporary is heated to 250°C in advance, and the high frequency power source (752) is heated with each gas flow stabilized and the internal pressure stabilized.
39) into the two-part electrode plate (736).
Power of atts (frequency l 3 , 5 G Mtlz)
was applied for about 4 hours, and a charge transport layer made of a plasma-polymerized ethylene film having a thickness of about 67 zm was formed on the conductive substrate (752). The plasma-polymerized ethylene film obtained as described above was subjected to Fourier transform infrared spectroscopy (manufactured by PerkinElmer),
-NMI'R device ([1 unit NM1υ manufactured by JEOL Ltd. and 'II-NMIt device (solid-state NMR manufactured by JEOL Ltd.)'
As a result of measurement and analysis in 3, it was found that in the chemical structure of the plasma-polymerized ethylene film, the ratio of the number of carbon atoms bonded to hydrogen, N1, to the number of carbon atoms, N1, that are not bonded to hydrogen, on the backside of carbons that have unsaturated bonds. N+:Nt was approximately 53:47, ie, l:0.89. Also, the electrical resistance of the dumb is 4
1-1, the dark resistance is approximately l x l Q 11
9 cm or less, and the light-dark resistance ratio was 10" to 104 or more. It was found that the plasma-polymerized ethylene film of the present invention can be used satisfactorily as an electrophotographic photoreceptor. (II) Electron 6:j generation layer (a-S Formation of i-layer) J&
After forming a plasma-polymerized ethylene film on the plate (1) by the process of ([), the electric power from the high-frequency power source (739) is applied to j11.
(The vehicle was then stopped and the inside of the reaction tank was evacuated. 3rd valve 1; σ 2nd valve (709) and (708)
5ill+gas from the third tank (703),
11. From the second tank (7G2). Gas output pressure gauge I
Kg/cm” under the mass [l-conte [1-la (71
5) It flowed into Nibi (714). , each mass flow control (11 pieces of 7-ra was prepared, the flow rate of 5Hr4 was set to 90sec, the flow rate of ■) was set to 'llosecm, and the reaction hl'/1.: was allowed to flow in. Each flow m After stabilizing, the internal pressure of the reaction tank (73:D) was adjusted to 0 'I' orr. With the gas flow rate stabilized and the internal pressure stable, the high frequency if!
1 (739) and applied 30 W power (frequency ¥5 (13,50 Mllz) to the electrode plate (736) to generate a glow discharge. This glow discharge was carried out for 10 minutes, and a -5i:I (A charge generation layer was formed. (, III) (Performance evaluation of photoreceptor) Through steps (1) and (11), the 7ti charge generation layer and the a-81 layer were formed with ΔQ
J, l: Performance evaluation of photoreceptors sequentially laminated on a plate was performed. The evaluation was carried out using the photoreceptor tester shown in Figure 14.
Chargeability and sensitivity were examined. The prepared photoreceptor sample $4 (35) was placed on a scanning table (37) and fixed with a shield cover (36). The scanning table (37) is moved to the charging area (52) and the high voltage supplied by the 17.7KV DC high voltage (40) is applied to the charger (42) and the sample (3
5) Corona discharge was performed on the surface. Next, the scanning table (37) was moved to the Ti-radiating area (51). The surface potential of the corona-charged sample is sensed by a transparent electrode (48), and its value is read by a surface potential meter (49) and output to a recorder (50). The photoreceptor of the present invention showed good charging ability. Next, the shutter (47) was opened, and the surface of the sample (35), which was being electrically charged, was irradiated with the light from the mirror (44) reflected by the light beam (43). Irradiation was performed using a transparent electrode (48
), and the change in surface potential due to irradiation is output to the recorder (50), and at that time, the flowing current is detected by the optical current monitor (38). The photoreceptor of the present invention has an initial surface potential (V ++) = -4'
) “1” at 5 volt, intense exposure! TkEl/
2 was approximately 0.71 ux-sec. Furthermore, a photoreceptor drum was manufactured in the same manner as in Experimental Example 1,
Minolta Camera Co., Ltd. copy machine (E I) -650Z
), good images were obtained. In addition, when the drum-type photoconductor tester (U and Z shown in the figure) was used to carry out the lithography process, the electrostatic charge, exposure irradiation, transfer, static elimination charge, and static elimination eraser tip irradiation were performed every 50 times. After repetition, stable static 7i characteristics were obtained. When forming the a-C layer, C, IL and 11. The flow rates were set to 100 sec and 805 ccrn, respectively, the internal pressure of the reaction tank was 1 and 2 torr, and the applied power was 23
Example 1 except that the reaction time was 5 hours.
17 5.5μ scraps, N, :N, is about 85
:15, that is, a plasma polymerized ethylene film of 10818 was obtained. The formation of the a-Si layer was performed in the same manner as in Example 1, and the thickness was 1
A μ shoulder R-9i layer was obtained. Performance evaluation of the photoreceptor obtained as described above (III)
), Vo"" -G I 0VO
IL%1; l/2=I O, 50, ux - sec
Met. In place of the plasma-polymerized ethylene 11 produced in step (1) of Example 1, a thick polyethylene film (I The polyethylene film was fabricated to a thickness of 6 μm, and step (II) was performed thereon. I'+: i As mentioned above, the number of carbons that eliminate unsaturated bonds is 5 to 50%.
It is about 0.1% out of the range. Further, the electrical resistance was about 101 oΩam, indicating that it was an insulator. Performance evaluation (Ill) of the obtained photoreceptor revealed that the photoreceptor had no photosensitivity, quickly charged up after several repetitions, and could not be used for electrophotography. A photoreceptor was prepared in which only an a-Si layer was formed on an aluminum 12 substrate. 3. The production was carried out under the same conditions as in Example 1.
The test was carried out for 25 hours to form 4 a-S layers with a thickness of 6.5 μat. When the performance of the photoreceptor was evaluated, it was found that a 1-minute band 1u capability could not be obtained with the polarity. In addition, from now on, Examples, Comparative Examples, and B will be produced only with flat plates,
Electrostatic properties and image properties: J1-1. Koi carp (1) Not shown in Fig. 13, in the decomposition device
First, the inside of the reaction chamber (733) was
After creating a high vacuum of 'l'orr culm, open the first and second jAI regulating valves (707) and (708),
Output pressure gauge l Kg/cm for Ctllt gas from the first tank (701) and Ut gas from the second tank (702).
Mass flow control (I-RA (70) and (7)
1A). And each mass flow controller
-ct- La scale, l, IJ adjustment, C2112 flow! It was set to G Osccm and fly to 80 seconds, and flowed into the reaction chamber (733). After each flow rate stabilizes, use a JA1 adjustment saw so that the internal pressure of the reaction chamber (733) becomes 0°8'l'orr. - For the conductive substrate (752), preheat to 200°C using a 2x50xjOxi aluminum plate, and turn on the high frequency power supply (739) when each gas flow j11 is stable and the internal pressure is stable. death? [i-force applying electrode (736)
85 watts of power (frequency 13.56 MrTZ)
Approximately H, 2I+! , , plasma polymerization was performed to form a conductive substrate (752) J- with a thickness of approximately 10 μm. N1 in this film: N t
was approximately 44:5 G, or l·1.27. (11) The application of power from the high frequency 71i source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated. The fourth and second regulating valves (710) and (708) are opened, and 5i11. gas, 2nd
Output pressure gauge IKg for I+ and gas from tank (702)
/c+n' mass flow control [1-ra (716)
It's Uo flowing into Onibi (714). Each mass [J-Adjust the scale of the controller by -1, and the flow I
11 to 90sec, 1 (2 flows to 2 I Os
ccm and flow into the reaction chamber. 3. After each flow 11t stabilized, the reaction chamber (733
) so that the internal pressure is I, 01'orr,'j7
,1 set up. When the gas flow n1 is stable and the internal pressure is stable, the can circumference θ is turned on, the power supply (739) is turned on, and the power application electrode (736) is
W's? Ii force (frequency 13, 56 MIIZ) was applied to generate a gas discharge. This glow discharge is 1
a-S i: 117(
! /+if generation layer was formed. The obtained photoreceptor had an initial surface potential (V O) −490
The half-decreased exposure m E l /2 when volL is 0, 5
(ux-sec) Also, when an image was formed on this photoreceptor and transferred, a clear image was obtained. Example 3 (1) In the glow discharge decomposition apparatus shown in Fig. 13,
4゛、I'or inside the reaction chamber (733)
After creating a high vacuum of about r, open the first to third regulating valves (70
7) or 7'09) and open the first tank (701).
) from Ct++4 gas, el from the second tank (702)
14 gas, 11. from the third tank (703). Gas was flowed into the mass flow controller (713) to 715) under the output pressure gauge IKg/cm2. Then, adjust the scale of each mass flow controller, and
, the flow rate is 45sccm, C1r4 is lOOscc
Set m and tlz to 20 sccm and flow into the reaction chamber (733). After the respective flow rates became stable and no, the internal pressure of the reaction chamber (7'A3) was adjusted to 1 Otorr. on the other hand,
Conductive J1 (as a plate (752), 2X50X50x
Using a 11-m aluminum plate, heat it to 250°C, and when the flow rate of each gas is stable and the internal pressure is stable, a high-frequency wave 711A;1 (739) is applied, and the power application electrode (
736), a power of 250 WattS (frequency rlII
: (, 50 MIIZ) was applied for about 5 hours to form a 6:r transport layer with a thickness of about 671 m. N + of the complaint: N t is 66.34, struck, 1
．． It was 0°52. A photoconductor was obtained, in which a photoreceptor 6:i generation layer was formed on its -L in (11) of Example 2. This photoreceptor has V u--520 volts, I; I/2=
1, 5 lux -5LIC. Furthermore, when images were formed and transferred, clear images were obtained. Example 4 (1) First, the inside of the reaction chamber (733) was heated using a glow discharge decomposition device (not shown in FIG. 13).
After creating a high vacuum of about rr, open the first to third regulating valves (7
07) or 709), and open the first tank (701).
) JS building 3 Cttl, gas, CIl gas from the second tank (702), Ilt gas from the third tank (703) under the output pressure gauge IKg/cm2 [! - flowed into the control [Nora (713) or 715]. Then, adjust the scale of each mass flow controller,
C71 (, the flow rate is G Osccm, Cl1a is G
OsccmSIIt was set to be lOOsccm and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.5 torr. On the other hand, as the conductive substrate (752), use an aluminum plate of 2 x 50 x 50 mm, heat it in advance to 250 ° C.
739) and 200 to the power application electrode (736).
Plasma polymerization was performed for about 5 hours by applying a power of 5 alts (frequency: 13.56 MIIZ) to form an electron 6:j transport layer with a thickness of about 5 μm! N I: N t in this film is approximately 32:C8, i.e. l
:2.1. A photoreceptor with a 6:1 generation layer shown in (11) of Example 2 formed thereon was obtained. This photoreceptor is ■. = -53
0 volt, El/2-about 1, 8 lux-sec
Met. Furthermore, when images were formed and transferred, clear images were obtained. Example 5 (+) In the glow discharge decomposition apparatus shown in FIG. 13, first, the inside of the reaction chamber (783) was heated to
After creating a high vacuum of about r, the first and second regulating valves (70
7) and (70g), and open the first tank (701).
From the second tank (702), H gas was flowed into the mass flow controllers (713) and (714) under an output pressure gauge of 1 kg/cll. Adjust the scale to set the flow m of C11 to 90 sccm and 11t to 180 sccm.
secm, and flowed into the reaction chamber (733). After each flow rate has stabilized, the reaction chamber (733
) was adjusted so that the internal pressure was 0°151'orr. On the other hand, as a conductive cylinder J, ζ tentative (752), 2x5
Preheat the aluminum plate on the shoulder of 0x50 to 350℃ once a month, and when each gas flow is stable and the internal pressure is stable, turn on the high frequency power supply (739).
A power of 300 WaLLS (frequency 13.56 M1lz) was applied to one electrode (7313) to perform plasma polymerization for about 10 hours, and the thickness of all carbon atoms contained on the conductive J1ζ plate (752) was about 6°. A charge transport layer of 5 μm was formed. N, :N, in this film is 22:T8, beaten, l:3
．． It was 5. A photoreceptor was obtained in which the TL charge generation layer shown in (11) of Example 2 was formed on the -L. This photoreceptor is
Vo-580volL, E l/2= 2, 812
It was ux-sac. In addition, when the image was created and transferred,
I could see a clear image. Example 6 (1) In the glow discharge decomposition apparatus shown in FIG. 13, first, the inside of the reaction chamber (733) was
After creating a high vacuum of about
) and (725), and OX gas from the 6th tank (706). Styrene gas was flowed from the container (719) into the mass tubes [J-controller (71 g) and (72 g). The 18th device (719) is the first heater (72
It was used after being heated to about 50°C according to 2). and,
Adjust the flow rate of styrene (cs+ta) to 50 sec,
secm, and flowed into the reaction chamber (733). After each flow fit became stable, the internal pressure of the reaction chamber (73a) was adjusted to 0.51'orr. on the other hand,
Conductive J, (for plate (752), 2X50X50m
Using an aluminum plate of 500 m, preheat it to 150°C, and when the flow rate of each gas is stable and the internal pressure is stable, the low frequency power supply (741) is turned on and the power application electrode (736) is heated to 150°C.
Plasma polymerization was performed for about 50 minutes by applying a power of 50 wa LLs (frequency 30 KI17.), and the conductive substrate (75
2) A charge transport layer having a thickness of about 8 μm was formed on the sample. Nl:Nt in the film is 72:25, i.e., l:
It was 0°33. A photoreceptor was obtained on which the 'fMd:j generation layer shown in (II) of Example 2 was formed. This photoreceptor has Vu = −G 20volt, l”]l/
2=4.01ux-st>c. Also image creation, transfer T
After 7 shots, a clear image was obtained. Effects of the Invention The FF machine plasma polymerized film according to the present invention is used as a charge transport layer #J
The photoreceptor has excellent charge transport properties and charging ability, and can obtain a sufficient surface potential even if the film is thin or thick, and can obtain good images. According to the invention, 71 lX! When A-5i is used in the j-generating layer, it is possible to obtain a thin film photoreceptor, which could not be achieved with the conventional A-8I photoreceptor. In the photoreceptor of the present invention, the raw materials thereof are inexpensive, the necessary eight layers can be formed in the same tank, and the film 19 can be thin, so the manufacturing cost is low (and the manufacturing time is short).
The plasma heavy metal film according to the present invention can be formed into a thin film without causing pinholes (i.e., can be formed homogeneously, so it can be easily made into a thin film. In addition, it has corona resistance and acid resistance. Since it has excellent moisture resistance, heat resistance, toner releasability and rigidity, the durability of the photoreceptor improves by 4 degrees when used as a surface protective layer.

[Brief explanation of drawings]

1 to 12 show schematic cross-sectional views of the photoreceptor of the present invention. FIG. 13 is a schematic diagram showing a photoreceptor manufacturing apparatus Kt. FIG. 14 is a schematic diagram showing a photoreceptor tester. The symbols in the figure are as follows. (1)...''1 (tentative) (2)...Charge transport layer (a-C layer) (3)...Electricity 6:j generation layer (4)...
- Overcoat layer (5)... Undercoat layer (701) - (706) - Tank (707) - (712) and (725) - (727) -
...Control valves (713) to (718) and (728) to (
7:(0)...Mass flow controller (719)-(721)...Container (732)...Main pipe (733)...Reaction chamber (735)...Ground electrode (736)...Paper Force applying electrode (739)...High frequency power supply (741)...Low frequency power supply<14:l) - Direct AtTl pressure source (747) to (750)...Vacuum pump (752)
Conductive substrate (35)...Trial, (36)...Shield cover (37)...Scanning table (38)...Photocurrent monitor (39)...Switch (40)...DC High voltage (41)...Total current monitor (42)...Charger (4a)...HaCl generator lamp (44)...Mirror (4
5)...Cold filter (46)...ND filter (47)...Shutter (48)...Transparent electrode (49)...Surface potential meter (50)...Recorder (51)・・Ift,
Coarse area (52)... Charged area Patent applicant Minolta Camera Co., Ltd. I11 Figure 43 Zero 7:! . s10wa

Claims (1)

[Claims] 1. In a functionally separated photoreceptor having a charge generation layer (3) and a charge transport layer (2), the charge transport layer (2) is an amorphous carbon film containing hydrogen and has unsaturated bonds in its chemical structure. Of the carbons that have, the ratio N_1:N_2 of the number of carbons bonded to hydrogen N_1 and the number of carbons N_2 not bonded to hydrogen is 1
:4 to 1:0.2.