JP2651283B2 - Seamless belt including laminate of conductive polymer layer and host polymer layer, and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a seamless polymer belt and a method for producing the belt. More specifically, the present invention relates to a seamless belt comprising a laminate of a host polymer layer and a conductive polymer layer, and to the electrochemical deposition of a conductive polymer from a dispersion or emulsion and the electrophoretic deposition of a host polymer on an electrode On the production of these belts. Furthermore, the present invention relates to electrophotographic and particle radiographic image forming members including these seamless belts, and to an image forming method using these members. One advantage of the belt of the present invention is that it separates the electronic conduction properties, and the physical and mechanical properties of the belt, provided by two different polymers, so that both properties can be independently controlled. Can be optimized.

[0002] Imaging members for electrophotographic imaging systems comprising a selenium alloy vacuum deposited on a hard aluminum support are known. These imaging members require sophisticated, highly complex and expensive manufacturing equipment. Alternatively, the imaging member is prepared by coating a rigid support with photoconductive particles dispersed in an organic thin film forming binder. The coating of the hard drum support is performed by various techniques such as spraying, dip coating, vacuum evaporation and the like. However, rigid drum imaging members have limited flexibility in device design, are not preferred for flash exposure and are expensive. Flexible organic imaging members are manufactured by coating a web, then cutting the web into segments, and forming the belt by welding the opposing ends of the cut web. However, a weld seam created on the imaging member interrupts the continuity of the outer surface of the imaging member and must be indexed so that it is not printed during the imaging cycle. Therefore, it has a bad influence on efficient continuous paper supply and throughput. This is because it is necessary to detect a seam within the length of each paper. The mechanical and optical equipment required for indexing is a copy machine,
Complicates copiers and printers, raises their costs,
And reduce design flexibility. Also, welded belts are undesirable for electrophotographic imaging member systems. This is because the seam is a weak point of the belt and will collect toner and paper dust during cleaning, especially when using a wiper blade cleaning device.

Accordingly, seamless belts are particularly desirable as electrophotographic and particle radiographic imaging member supports. Further, a seamless belt exhibiting conductivity is particularly desirable as a support for electrophotographic and particle radiographic imaging members. This is because the conductive portion of the support can function as a base plane for the imaging member. The present invention provides seamless belts that exhibit electrical conductivity on one surface, and these belts are suitable as supports for imaging members.
Further, the seamless belt of the present invention is suitable as an image receptor for a particle radiographic image forming method in which a latent image is formed on a dielectric image receptor by ion attachment. This method is disclosed in U.S. Pat. Nos. 4,524,371 and 4,463.
363, which is incorporated herein by reference.

[0004] One layer of the seamless belt of the present invention is prepared by electrochemically depositing a conductive polymer on an electrode. An electrochemical polymerization method for conducting polymerization of pyrrole, which is conductive, is disclosed in US Pat. No. 4,547,270.
The disclosure of which is incorporated herein by reference. This document describes that pyrrole or a mixture of pyrrole and a comonomer is electrochemically polymerized by anodic oxidation of a monomer in the presence of a conductive salt in a solution or dispersion of an electrolyte solvent, and the pyrrole polymer is deposited at the anode. A method is disclosed. The anode used consists of a non-conductive sheet material which can be impregnated with an electrolyte, one or more conductive supports and contact strips which are electrically connected to a current supply to the anode.

Further, US Pat. No. 4,680,236 discloses an electrodeless heterogeneous polypyrrole material comprising a host polymer and polypyrrole deposited on and inside the host polymer. The insulating polymer is at least partially immersed in a sufficient amount of pyrrole monomer so that the monomer becomes conductive after polymerization. This polymerization is a chemical oxidative polymerization (dip-polymerization)
Wherein, when carried out under anhydrous conditions, the insulating polymer is converted into a semiconductive material consisting essentially of a first type of conductive polypyrrole and a host polymer comprising a halide counterion of a Group VIII metal. is there. Thereafter, a second type of conductive polypyrrole is electrically deposited on the semiconductive material containing the counter ion. The composite material having the two kinds of polypyrroles and anions is used in applications where a lightweight organic resistive heating element is desired.

Further, US Pat. No. 4,617,228 discloses a method of making a conductive material. The dielectric porous material and the conductive material comprising a pyrrole polymer in the pores of the material comprise treating the porous material with liquid pyrrole,
It is prepared by treating the resulting porous material with a solution of a strong oxidant in the presence of a non-nucleophilic anion. The pyrrole monomer is oxidized to a pyrrole polymer, which deposits in cracks in the porous material. Alternatively, the dielectric porous material is first treated with a solution of a strong oxidant and a non-nucleophilic anion, followed by treatment with liquid pyrrole to deposit conductive polypyrrole into the pores of the material. The resulting porous material, including polypyrrole, is conductive while other properties of the porous material are not substantially affected.

Further, US Pat. No. 4,697,000 teaches treating a liquid pyrrole with a solution of a strong oxidant that can oxidize the pyrrole to a pyrrole polymer, and providing a substantially non-nucleophilic anion. Discloses a method for producing a conductive polypyrrole powder, wherein the pyrrole is oxidized by an oxidant in the presence of to precipitate the conductive polypyrrole powder. The strong oxidant and the non-nucleophilic anion can be derived from a single compound. This anion is
It plays a role as a trace additive of polypyrrole. This reaction can be performed in an aqueous solution or an organic solvent.

The host polymer layer of the belt of the present invention is produced by electrophoretically depositing a host polymer on an electrode. U.S. Pat. No. 4,760,105, which is incorporated herein by reference, is dispersible or emulsified in water,
Disclosed is an emulsion having a discontinuous phase, comprising an epoxy resin having at least two epoxy groups, a water-soluble salt of an imide compound having at least one carboxyl group, and a crosslinking agent, wherein the discontinuous phase comprises: Has excess epoxy functionality. The continuous phase is water. A method for forming a coating on a conductive support is also disclosed in this patent. The support and electrodes are immersed in the emulsion and a direct current is applied between the support and the electrodes to electrophoretically deposit the coating on a support of epoxy resin, imide compound and crosslinker. The support is removed from the emulsion and heated to a sufficient temperature to cure the coating.

Further, cited as the contents of the present specification,
"An Electrically Conductive Plasti" by M.De Paoli et al.
c Composite Derived from Polypyrrole and Poly (viny
l Chloride) "Journal of Polymer Science, Vol. 23 p
ages 1687-1698 (1985) contains poly (vinyl chloride)
A method is disclosed for obtaining a conductive plastic material by electrochemically polymerizing pyrrole in a matrix to form a material in which polypyrrole is uniformly distributed in a poly (vinyl chloride) matrix. further,
"Co," by M. De Paoli et al., Which is incorporated herein by reference.
nductiveComposites from Poly (vinyl Chloride) and P
olypyrrole "J. Chem. Soc., Chem. Commun., page 101
5-1016 (1984) discloses a method of electrochemically polymerizing pyrrole on a platinum electrode covered with a poly (vinyl chloride) thin film to form a composite laminated polymer thin film.

[0010] William W. Limburg, Santokh S. Badesh
a, and John S. Facci's "Seamless Conductive Sub
strate for Electrophotographic Applications, "Xero
x Disclosure Journal, Vol. 14, No. 2 (1989) discloses a conductive support comprising an interpenetrating polymer network comprising conductive polypyrrole in a host polymer such as polyvinyl chloride. This interpenetrating network deposits the host polymer on a cylindrical metal electrode by electrostatic powder or solvent spraying, followed by
Manufactured by immersing the host polymer and conductive mandrel in a bath containing a solution of pyrrole in the electrolyte, anodically electropolymerizing the pyrrole, and attaching conductive polypyrrole to the entire void region of the host polymer. can do. Alternatively, pyrrole can be oxidatively polymerized almost instantaneously to polypyrrole by contacting the pyrrole-welded host polymer with diethyl selenite. In addition, the polypyrrole interpenetrating network allows the swelling solvent diethyl selenite solution and pyrrole solution to diffuse into the host polymer from opposite sides of the thin film, respectively, and oxidative chemical polymerization of pyrrole inside the host polymer where each solution intersects. Can be prepared.

The materials and methods described above are useful for their intended purpose, but are flexible, self-supporting conductive polymer thin films, and, in particular, electrostatic imaging members and particle radiographic imaging. There is a need for improved seamless belts that can be used for various applications, including support for members. It also separates the conductive function from the support function (functions derived from polymer properties such as flexibility, tensile strength and elongation modulus) and optimizes the belt conductivity and physical properties independently of each other. There is a need for a conductive seamless belt that can be converted.

It is an object of the present invention to provide an improved flexible, flexible polymer seamless belt.

The present invention achieves this object by providing a conductive material.
Includes laminate of conductive polymer layer and host polymer layer
At least one surface of the belt has a resistivity of about 10^Two ~
About 10 ⁶ Ohms / square (Ω / □), preferably
This resistivity is about 10^Five Ω / □ or less seamless bell
To provide The seamless belt of the present invention comprises the following steps
It can be produced by a method comprising: (1) a non-aqueous solvent,
Electrolyte and monomer that becomes conductive polymer when polymerized
(2) preparing a solution containing
Pole, a step of adding to the electrolytic cell including the counter electrode and the reference electrode,
(3) Start by applying potential to the working electrode and the counter electrode.
The anodic oxidation and polymerization of these monomers are conducted using conductive polymer materials.
(4) solution until the material layer adheres to the working electrode
Polymer charged in solid dispersion medium and liquid dispersion medium
Preparing a dispersion liquid containing (5) a layer of a conductive polymer
With working electrode and counter electrode electrochemically attached
Adding the dispersion to the tank, (6) applying a potential difference to the working electrode
Onto the working electrode caused by applying
Electrophoretic deposition of the host polymer
Layer adheres on top of the conductive polymer present on the working electrode
(7) Subsequently, the working electrode is heated and
Forming a two-layer laminate by (8)
This is the step of separating this laminate from the poles.

Further, the present invention provides an image forming member including a support and a photogenerating layer, wherein the support comprises:
Comprises a laminate of a conductive polymer layer and a host polymer layer, the surface of the laminate in contact with the photogenerating layer, about 10 ²
Exhibit a conductivity of about 10 ⁶ Ω / □. Further, the present invention provides
Provided is an image forming method, which comprises incorporating an image forming member into a particle radiographic image forming apparatus, forming a latent image on the image forming member by ion attachment, and forming a latent image by toner. Developing, transferring the developed image to a support, and permanently fixing the transferred image on the support, wherein the imaging member includes a laminate of a conductive polymer layer and a host polymer layer, at least one surface of the belt, showing about 10 ² to about 10 ⁶ Omega / □ conductivity of.

As used herein, the term "laminate" refers to a structure consisting of discrete, discrete layers. The seamless belt of the present invention has the unique advantage of allowing the separation of the conductive function from the physical properties of the host polymer due to the conductive polymer layer / host polymer layer laminate feature. The separation of these functions makes the selection of the desired polymer properties, such as creep, compliance, tensile strength, etc., independent of the electronic properties of the host polymer, thereby making the material used in the seamless belt of the present invention. Significantly expand the selection range. For example, many conductive polymers form brittle or poorly self-holding thin films. The laminate of the conductive polymer layer and the host polymer layer can retain the excellent physical properties of the host polymer and the conductivity of the conductive polymer. Furthermore, by the electrochemical technique, the conductive seamless transparent laminate can be completely formed, and by forming this laminate,
Significant cost, hardware and space savings are obtained. Thus, the seamless belt of the present invention makes it possible to construct an imaging member that is translucent and capable of erasing residual charge from the back or bottom. By having the ability to erase from the back side, the imaging member can provide significant space savings in the imaging device. This is because the erase lamp can be located inside the belt instead of near the outer surface.

The seamless belt of the present invention is prepared by electrophoretic deposition of a host polymer from an emulsion or dispersion, by deposition of a conductive polymer onto an electrode by continuous electroanode or electrochemical deposition from solution. , Can be manufactured. Electrical deposition of the conductive polymer is achieved by anodic oxidation of the monomer precursor at the anode in an electrolyte containing the monomer precursor. For example, when the conductive polymer is poly (pyrrole), the pyrrole monomer is anodized as follows.

[0017]

Embedded image

Oxidation causes the monomers to polymerize and become insoluble and adhere to the electrodes. The resulting polymer attachment layer is conductive.

A dispersion or emulsion of the host polymer particles charged with an organic solvent is prepared, and an electric field is applied between the electrodes until an adhesion layer of the polymer particles is formed on the electrodes. Electrophoretically adhere.

According to one method of making the seamless belt of the present invention, a thin layer of a conductive polymer is first electrochemically deposited on an electrode, followed by electrophoretic deposition of a host polymer emulsion on the electrode. I do. Subsequently, by heating the electrodes, the host polymer particles are coalesced to obtain a transparent, seamless polymer laminate having a conductive surface.

In the present invention, the conductive polymer of the belt is attached to the electrode by an electrochemical attachment method. Generally, this method is performed using a conventional three-electrode cell in which the working electrode is a seamless cylindrical mandrel. This mandrel may be solid or hollow,
If hollow, the electroadhesion may occur on either the inner or outer surface of the cylinder. If it is preferred that the deposition occur on the inner surface of the hollow working electrode, the counter electrode will generally be a seamless cylindrical shape with a smaller diameter than the working electrode, such that the cylinder of the counter electrode concentrically coincides with the inside of the working electrode. It is a mandrel sleeve. If it is preferred that the deposition occur on the outer surface of the cylindrical electrode, the working electrode (anode) is a seamless cylinder made of a material such as nickel,
The cylinder of the counter electrode is a cylindrical sleeve made of a material such as nickel that is larger in diameter than the working electrode and is placed concentrically around the working electrode. The standard electrode is a standard saturated calomel electrode (SCE), a saturated sodium calomel electrode (SSCE), or the like. The reference electrode is located between the working electrode and the counter electrode, preferably in an annular space near the working electrode. The opening between the working electrode and the counter electrode may be any reasonable distance, but is preferably about 1 to about 10 cm.

Any suitable material having a conductive outer surface can be used for the counter and working electrodes onto which the polymer component of the belt of the present invention is deposited. The electrode must be dimensionally and thermally stable at the temperature of the manufacturing process, insoluble in the organic solvents used in the electrode deposition process of the present invention, and must be a host polymer particle, conductive polymer, or dispersion mixture. Must not react chemically with other components. Typical electrode materials include stainless steel,
There are metals such as nickel, chromium, brass, and platinum. Typical ceramic electrode materials include ceramic, glass, etc. coated with a conductive coating. These electrodes are
It can be formed into a desired shape by an extrusion method, a molding method, a blow molding method, an injection molding method, a cast molding method, or the like. A preferred electrode is an electroformed nickel mandrel sleeve manufactured by electroplating of nickel from a bath containing nickel.

In general, the electrodes may be cylindrical in shape, hollow or solid. The electrode surface to which the polymer is applied may be the inner surface (polymer applied to the hollow or solid outer surface) or the outer surface (polymer applied to the hollow inner surface) of the belt loop formed by the method of the present invention. Functions as a mold surface. In other words, the particles may be deposited on either the outer surface of the cylindrical electrode or on the inner surface of the hollow cylindrical electrode.

If necessary, a release agent may be applied to the electrode surface before the layer forming the seamless belt is attached. Typical release agents include silicones (eg, E-155 silicone release coating and F-5
SWSF-544 cured with 46 catalyst (both SWS
Silicones) and Dow Corning 20,
(Available from Dow Corning).

When a release coating is used, the release coating is preferably applied to the cleaned electrode surface.
Prior to the application of the release coating, the usual industrial processes, such as metal polishing of the electrodes, chemical cleaning, solvent cleaning and degreasing, can be performed. Depending on the state of the electrode surface, it is desirable to remove dirt, dust, mill scale, paint, oil, and the like. Typical coating techniques include
There are a dip coating method, a spray coating method, a brush coating method and the like.

Instead of treating the working electrode with a stripper, the nickel electrode is placed in a 50:50 mixture of hydrogen peroxide and ammonium hydroxide, approximately one-half, prior to deposition of the conductive polymer.
It may be processed by soaking for a time. Also, before electrodeposition, the electrodes, for example, grit paper,
It may be polished with steel wool, diamond paste or the like.

To effect the electrochemical deposition of the conductive polymer, the corresponding monomer is dissolved in a suitable solvent, which is generally a non-aqueous anhydrous polar aprotic solvent. Prior to dissolution, the monomers can be purified, for example, through an alumina chromatography column.
Examples of suitable solvents include anhydrous acetonitrile, dimethylformamide, dimethylsulfoxide, butyronitrile, benzonitrile, dimethoxyethane, N-methylpyrrolidinone, and the like, and mixtures thereof. The monomer is dissolved in the solvent to a concentration of about 1 millimolar to about 0.3 molar, preferably about 0.1 to about 0.3 molar. The solution also generally contains from about 0.05 mole to about 1 mole of electrolyte, preferably from about 0.5 to about 1.0 mole. The suitable electrolyte is an ionic compound whose cation is, for example, sodium, lithium,
Potassium, tetraphenyl arsenic, alkyl group of 1 to about 4
Selected from components such as tetraalkylammonium having one carbon atom, the anion being non-nucleophilic, for example, antimony hexafluoride, arsenic hexafluoride, tetraphenylborate, phosphorus hexafluoride, perchlorine It is selected from components such as acid salts. Examples of suitable electrolytes include tetraethylammonium perchlorate, sodium perchlorate, lithium perchlorate, and the like.

[0028] Polymerization occurs when a constant potentiostat voltage of about 0.75 to about 1.5 V is applied to the cell, and typically about 1-2 mA / cm ² is obtained here. The conductive polymer undergoes anodic interfacial electrodeposition and adheres to the anode. The voltage is applied until the conductive polymer has deposited on the working electrode to the desired thickness. The desired thickness of the conductive polymer layer will generally range from about 200 Angstroms to about 1 micron, preferably from about 1000 Angstroms to 2000 Angstroms, when a support for an electrophotographic or particle radiographic imaging member is intended. Angstrom. Typically, applying the voltage for about 1 to about 10 minutes provides the desired thickness. It may be convenient to correlate the thickness to the amount of charge consumed at the working electrode. This is because the electric charge (Q) consumed is the current (i) and the time (t)
Because it is equal to the product of

Q = i × t

The thickness of the layers and the charge consumed can be determined experimentally for the particular system used. For example, a 2500 Angstrom thick layer would be:
This corresponds to a charge consumption of about 0.25 coulomb / cm ² . This increase in density increases the deposition rate and reduces the time required to achieve the desired thickness.

Examples of suitable conductive polymers for the seamless belt of the present invention include poly (heteroenes) such as poly (pyrrole) and poly (N-alkyl) pyrroles such as poly (N-methylpyrrole). , Poly (2,5-thienylene), poly (3-methyl-2,5-thienylene)
And poly (2,2′-bithiophene), polyaniline, and heterocyclic conductive polymers.

A more detailed description of the method of electrochemically polymerizing materials such as polypyrroles is disclosed in US Pat. No. 4,547,270, which is incorporated herein by reference.

Following deposition of the conductive polymer layer, the working and counter electrodes with the deposited layer are rinsed to remove excess solvent and electrolyte. Generally, the working and counter electrodes having a conductive layer are first rinsed with the solvent used during the electrochemical deposition process, followed by a rinse with another solvent, eg, ethanol. Subsequently, the working electrode and the counter electrode are incorporated in a normal two-electrode cell, which is essentially the same as the three-electrode cell described in the electrochemical deposition of the conductive layer, except that there is no reference electrode. Is the same. The layer of conductive polymer present on the working electrode is sufficiently conductive to allow electrophoretic deposition of the layer of host polymer on the electrode by the following steps.

[0034] The host polymer is dispersed in a suitable liquid dispersion medium. In general, a suitable liquid dispersion medium will be defined for each polymer, which will disperse the polymer as small particles, rather than precipitating the polymer as large amorphous masses. Also, in general,
The liquid dispersion medium is such that when a polymer is dispersed in the liquid, the polymer is electrostatically charged. The concentration of the host polymer in the liquid dispersion medium is generally from about 0.1 to about 2% by weight, with the closer to the upper end of the range, the more desirable. Suitable liquid dispersion media include solvent / non-solvent combinations, for example, propylene carbonate, dimethylsulfoxide, N-alkylpyrrolidones such as N-methylpyrrolidone, dialkylformamides such as dimethylformamide, dimethylacetamide. Dialkylacetamides such as N-alkylformamides such as N-methylformamide, N-alkylacetamides such as N-methylacetamide, alkyl ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetonitrile, propionitrile and butyronitrile. And the like. For example, when the host polymer is polyvinyl fluoride or polyvinylidene fluoride, a preferred liquid dispersion medium is propylene carbonate. For host polymers such as poly (amide-imide) and polyimide, a preferred liquid dispersion medium is a solvent such as a solvent comprising dimethylsulfoxide and an amine, e.g.
Methylpyrrolidone, dimethylformamide, dimethylacetamide, N-methylformamide, N-methylacetamide and the like and non-solvents include acetone, methylethylketone, methylisobutylketone, acetonitrile, propionitrile, butyronitrile and the like. A dispersion is formed by adding the host polymer to the solvent and the mixture to a suitable non-solvent. Suitable non-solvents are
The polymer is not soluble, but is compatible with the liquid dispersion medium and contains materials such as aliphatic nitriles and ketones. About 21 to about 33% by volume of non-solvent, preferably
The addition of about 28% by volume forms a dispersion containing the host polymer particles in the liquid dispersion at a concentration of about 0.1 to about 1% by weight, preferably about 1% by weight. The polymer is charged by adding the polymer to the liquid dispersion medium.

Next, the dispersion liquid of the host polymer is added to the electrolytic cell, and a voltage is applied between the electrodes. The working electrode is charged positively (anode) or negatively (cathode) depending on the selected host polymer. For example, polyvinyl fluoride adheres to the cathode, which places a negative charge on the working electrode when using this polymer. On the other hand, as the polyvinylidene fluoride adheres to the anode, the working electrode is positively charged to deposit the polymer. Polyimide and poly (amide-imide) also adhere to the anode. Generally, about 20
Apply a relatively low current density of 〜90 μA / cm ² .
The applied voltage is generally from about 10 to about 150V, preferably from about 10 to about 50V. The voltage is applied until a desired thickness of the host polymer layer is deposited. When intending to manufacture a support for an electrophotographic or particle radiographic imaging member, the desired dry film thickness of the host polymer layer will generally be
From about 1 mil to 4 mils, preferably from about 2 mils to about 3 mils. Typical times are from about 10 minutes to about 35 minutes. In many cases, the deposition rate is about 1/5 mil / min, but this deposition rate is not linearly related to processing time.
This is because the deposition rate decreases with time due to the insulating effect of the deposited host polymer layer.

Suitable host polymers are chloro, bromo or fluoro substituted polyvinyl compounds, such as polyvinyl fluoride, polyvinylidene fluoride (available from, for example, Pennwalt) and polyvinyl chloride, polycarbonate (eg Makrolon 5705). , B
ayer Chemical, Merlon M39, MobeyChemical, Lex
an145, General Electric Company), polyester (eg, PE-100 and PE-200, Goodyear Tire and Rubber)
Corporation), polyarylate, polyarylsulfone, polyethersulfone, polyimide, epoxy, poly (amide-imide) (Torlon 4000TF and Torlon 4000 T10,
Amoco Chemical Co., Copolyester (Kodar Copolyes)
ter PETG 6763, Eastman Kodak), polyaryl ethers and the like and mixtures thereof. The polycarbonate polymer is produced, for example, from the following compound. 2,2-
Bis (4-hydroxyphenol) propane, 4,4 '
-Dihydroxydiphenyl-1,1-ethane, 4,4 '
-Dihydroxydiphenyl-1,1-isobutane, 4,
4'-dihydroxydiphenyl-4,4-heptane,
4,4'-dihydroxydiphenyl-2,2-hexane, 4,4'-dihydroxytriphenyl-2,2,2
-Ethane, 4,4'-dihydroxydiphenyl-1,1
-Cyclohexane, 4,4′-dihydroxydiphenyl-β-β-decahydronaphthalene, cyclopentane derivatives of 4,4′-dihydroxydiphenyl-β-β-decahydronaphthalene, 4,4′-dihydroxydiphenylsulfone, and the like Is a mixture of Suitable host polymers are generally capable of forming a dispersion or emulsion of thermoplastic film-forming polymer particles that are charged and dispersed in an organic liquid dispersion medium. "Dispersion" herein
The term "refines a material and generally results in a diameter of about 1
It is defined as fine particles of less than or equal to 00 microns, with these particles dispersed in a liquid medium such that the fine particles do not directly contact each other. Particularly preferred are poly (vinyl fluoride), poly (vinylidene fluoride), polyimide, poly (amide-imide) and epoxy.

After becoming electrostatically charged, the host polymer particles are allowed to migrate through the organic liquid medium of the dispersion under the influence of an electric field, forming a uniform particle coating on the electrode. Thus, the host polymer particles have an electrical resistivity of at least about 10 ⁵ Ω-cm. Further, after the host polymer particles have been deposited on the electrode, they can coalesce to form a continuous thin film. When the coating of the particles on the mandrel is heated to coalesce the particles to form a continuous thin film and evaporate the organic solvent, the host polymer particles are only partially coalesced, if desired, and subsequently Can be cured. Typical examples of the curable thin film-forming polymer material include prepolymers such as polyimide, poly (amide-imide), polyurethane, epoxy, polyester, acrylic derivative, and alkyd. Generally, the host polymer particles in the dispersion have an average particle size of between about 0.01 and about 10 microns, and will remain in the dispersion during practical working times.

For a detailed description of a method for electrophoretically depositing a polymer from a dispersion, see US Pat.
No. 60,105, 4,664,768, 4,642
No. 170, 4,533,448, 4,474,658
And 4,425,467, which are incorporated herein by reference.

After electrophoretically depositing the host polymer on the working electrode, the resulting laminate is subsequently cured by heating the electrode. Generally, the details of the heating method are determined by each individual host polymer, but are smooth and uniform, and include bubbles, depressions, run,
The thickness is determined so that a thin film free from defects such as pinholes is formed. Generally, the heating time is from about 20 to about 90 minutes, and generally the preferred drying temperature is from about 160 to about 280
It is in the range of ° C. For example, if the host polymer is polyvinyl fluoride or polyvinylidene fluoride, the working electrode may be in an oven, in a closed atmosphere, at about 5
Heat at about 180 ° C. for minutes. This closed atmosphere is
The atmosphere in which the liquid dispersion medium vapor is present. For example, if the working electrode is a hollow cylinder and the deposition is on its internal surface, the laminate can be heated in a closed atmosphere by covering the top of the electrode with a plate and placing it in an oven. . After heating in a closed atmosphere, the laminate in which the host polymer is polyvinyl fluoride or polyvinylidene fluoride is heated in an oven at about 180 ° C. for about 15 minutes in an open atmosphere to generally coat the laminate from the electrode. Can be achieved by removing When the host polymer is a poly (amide-imide), the resulting laminate is treated at about 70 ° C to about 1 ° C.
Heating at 00 ° C for about 5 to about 10 minutes in an open atmosphere;
Subsequently, it is heated in an open atmosphere at about 180 ° C. to about 190 ° C. for about 1 hour. The belt thus formed can be peeled off from the working electrode.

The seamless belt of the present invention is suitable for use as a conductive support in an electrophotographic imaging member. After removing the belt from the electrodes, additional layers can be added to the belt of the present invention to produce such a member. These layers are generally applied to the conductive surface of the belt and include a blocking layer, an adhesive layer,
Photoconductive layers or combinations of these layers, or other additional layers may be included.

One or more suitable blocking layers can be added as one of the imaging member coatings of the present invention. A typical blocking layer is gelatin (eg, Gelatin 225, K) dissolved in water and methanol.
nox Gelatine) and Carboset 515 (BFGoodrich
Chemical Co.), polyvinyl alcohol, polyamide, gamma-aminopropyltriethoxysilane, etc. alone,
Or a mixture thereof. The blocking layer is generally
It has a thickness from about 0.01 micron to about 2 microns, preferably from about 0.1 micron to about 1 micron. However,
A thickness outside this range may be selected as long as the object of the present invention can be achieved. This blocking layer is applied using a suitable liquid carrier. Typical liquid carriers are water, methanol, isopropyl alcohol, ketones, esters, hydrocarbons and the like.

A suitable adhesive layer can be added as one of the imaging member coatings of the present invention. Typical adhesive layers include polyester, for example, du Pont 49,000 (EI
du Pont de Nemours & Company), poly (2-vinylpyridine), poly (4-vinylpyridine) and the like. Generally, the adhesive layer has a thickness from about 0.05 micron to about 2 microns, and preferably from about 0.1 micron to about 1 micron. However, a thickness outside this range may be selected as long as the object of the present invention can be achieved. This adhesive layer can be applied using a suitable liquid carrier. Typical liquid carriers include methylene chloride, methanol, isopropyl alcohol, ketones, esters, hydrocarbons and the like.

One or more suitable photoconductive layers
It can be added as one of the imaging member coatings of the present invention. The one or more photoconductive layers can include an inorganic or organic photoconductive material. Typical inorganic photoconductive materials include known materials such as amorphous selenium, trigonal selenium, selenium alloy, halogen-doped selenium alloy (eg, selenium-tellurium, selenium-tellurium-arsenic, selenium-arsenic, etc.), In addition, there are cadmium sulfoselenide, cadmium selenide, cadmium sulfide, zinc oxide, titanium dioxide and the like. The inorganic photoconductive material is
Usually, it is dispersed in a film-forming polymer binder. Examples of suitable binders include poly (N-vinyl carbazole), polyvinyl butyral, polystyrene, phenoxy resin,
Examples include polycarbonate, polyethylene terephthalate, poly (N-vinylpyrrolidinone), and polyvinyl alcohol. Typical organic photoconductive materials include phthalocyanine, quinacridone, pyrazolone, polyvinyl carbazole, 2,4,7-trinitrofluorenone, anthracene, and the like. Many organic photoconductive materials can also be used as particles dispersed in a resin binder. Generally, the photoconductive material is present in the range of about 5 to about 80% by weight, and the binder is present in the range of about 20 to about 95% by weight.

Also, suitable multilayer light guides can be used in the imaging members of the present invention. Multilayer light guides
It includes at least two electrically functional layers, a photogenerating or charge generating layer, and a charge transfer layer. The charge generation layer, charge transfer layer and other layers are added in any suitable order to produce a photoreceptor that is either positively or negatively charged. For example, a charge generating layer can be added before the charge transport layer as described in US Pat. No. 4,265,990, or as described in US Pat. No. 4,346,158. To
A charge transfer layer can be added before the charge generation layer. The entire description of these patents is cited as the content of the specification.

The photogenerating layer may include a single layer or a multilayer containing an inorganic or organic composition. One example of a generating layer is disclosed in US Pat. No. 3,121,006, in which finely divided particles of a photoconductive inorganic compound are dispersed in an insulating organic resin binder. . Useful binder materials described in this patent are those that can hardly transport the injected charge carriers formed by the photoconductive particles. As a result, the photoconductive particles must have substantial contact between adjacent particles in the layer for the purpose of enabling the elimination of the charge required for the cycling operation. Therefore, in order to obtain sufficient contact between the photoconductive particles and the particles to discharge quickly, usually about 50% by volume is used.
Is required.

Examples of the light generating layer include trigonal selenium, alloys of selenium containing tellurium, arsenic, etc. as components, amorphous silicon, various phthalocyanine pigments, for example, disclosed in US Pat. No. 3,357,989. Metal-free phthalocyanine X form, metal phthalocyanine such as phthalocyanine copper, quinacridone (trade name Mona
stral Red, Monastral violet and Monastral Red Y,
du Pont), substituted 2,4-diaminotriazines, polynuclear aromatic quinones, and India First Violet Lake B disclosed in U.S. Pat. No. 3,442,781.
dofast Violet Lake B), Indofast Brilliant Scarlet and Indofast Orange.
Examples of photosensitive members having at least two electrically functional layers include U.S. Pat. Nos. 4,265,990 and 4,23.
3,384, 4,306,008 and 4,299,
No. 897, a charge generating layer and a diamine containing transport layer member; U.S. Pat. No. 3,895,944, a dye forming layer, and oxadiazole, pyrazolone, imidazole, bromopyrene, nitrofluorene. And a hydrazone-containing charge transport layer member disclosed in U.S. Pat. No. 4,150,987, and U.S. Pat. No. 3,837,851. And a charge transport layer member containing a triarylpyrazoline compound. The descriptions of these patents are incorporated by reference in their entirety.

The photogenerating layer comprising the photoconductive composition and / or pigment and the resin binder material generally has a thickness of about 0.1
It ranges from microns to about 5.0 microns, and preferably ranges from about 0.3 microns to about 1 micron. Thicknesses outside these ranges can be selected as long as the object of the present invention can be achieved. The photogenerating composition or pigment can be present in the film forming polymer binder composition in various proportions. For example, about 10% by volume to 60%
% Of the photogenerating pigment by about 40% to about 90% by volume.
From about 20% to about 30% by volume of the photogenerating pigment can be dispersed in about 70% to about 80% by volume of the film-forming polymer binder composition. It can be dispersed in the composition. The particle size of the photoconductive composition and / or pigment should be less than or equal to the thickness of the solidified layer, and more preferably between about 0.01 micron and about 0.5 micron to provide a uniform coating. Can be promoted.

A suitable transport layer can be added as one of the imaging member coatings of the present invention to form a multilayer light guide. The transport layer may include a film-forming polymer binder and a charge transport material. Preferred multilayer light guides have a charge generation layer comprising a layer of photoconductive material and one or more compounds of general formula I dispersed therein in about 25% to about 75% by weight and having a molecular weight of about 20,000 to about 120,000. 000, comprising an adjacent charge transport layer of a polycarbonate resin material, wherein the photoconductive layer exhibits the ability to photogenerate and inject holes, and the charge transport layer Is
The photoconductive layer generates holes, and the holes generated by light,
In the region of the spectrum to be injected, it is substantially non-absorbing, but can aid in the injection of photogenerated holes from the photoconductive layer and transport the holes through the charge transport layer.

[0049]

Embedded image

A charge transport layer capable of injecting photogenerated holes in the charge generation layer and capable of transporting holes through the charge transport layer, represented by the foregoing structural formula:
And other examples of charge transporting aromatic amines include:
N, N'-bis (alkylphenyl)-[1,1'-biphenyl] -4,4'-diamine (where alkyl is
For example, methyl, ethyl, propyl, N-butyl and the like. ), N, N′-diphenyl-N, N′-bis (chlorophenyl)-[1,1′-biphenyl] -4,4′-
Diamine, N, N'-diphenyl-N, N'-bis (3
"-Methylphenyl)-(1,1'-biphenyl)-
4,4'-diamine and the like, which are dispersed in an inert resin binder. Examples of these transport materials are disclosed, for example, in Stolka et al., US Pat. No. 4,265,990, the entire description of which is incorporated herein by reference. Another example of a charge transport layer that can help inject the photogenerated holes in the charge generation layer and transport holes through the charge transport layer is tri-dispersed in an inert resin binder. Examples include phenylmethane, bis (4-diethylamine-2-methylphenyl) phenylmethane, 4 ′, 4 ″ -bis (diethylamino) -2 ′, 2 ″ -dimethyltriphenylmethane, and the like. For example, US Pat. No. 3,121,006
Many inert resin materials can be used in the charge transport layer, including those disclosed in US Pat.
This entire description is incorporated herein by reference. The resin binder used in the charge transport layer may be the same as the resin binder material used in the charge generation layer. Typical organic resin binders include thermoplastics and thermosets, for example, polycarbonate, polyester, polyamide,
Polyurethane, polystyrene, polyaryl ether,
Polyarylsulfone, polybutadiene, polysulfone, polyethersulfone, polyethylene, polypropylene, polyimide, polymethylpentene, polyphenylene sulfide, polyvinyl acetate, polysiloxane, polyacrylate, polyvinyl acetal, polyamide, polyimide, amino resin, phenylene oxide resin, terephthalic acid Resin, epoxy resin, phenolic resin, polystyrene-acrylonitrile copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylate copolymer, alkyd resin, cellulose film former (former), poly (amide-imide), styrene-butadiene copolymer, vinylidene Chloride-vinyl chloride copolymer, vinyl acetate-vinylidene chloride copolymer , Styrene - there alkyd resin. These polymers may be block, random or alternating copolymers.

In general, the thickness of the solidified transport layer is about 5 to
Thicknesses between about 100 microns, but outside this range can also be used. The charge transport layer must be insulating enough that in the absence of illumination, the static charge on the charge transport layer does not move at a speed sufficient to prevent the formation and retention of the electrostatic latent image. . Generally, the ratio of the thickness of the solidified charge transport layer to the charge generation layer is from about 2: 1 to about 20
0: 1 is preferred, but in some cases 4: 1
It may be as large as about 00: 1.

Generally, the charge blocking layer is about 0.0
It has a thickness of 5 to about 5 microns. The charge blocking layer prevents charge injection from the conductive layer into the photogenerating layer and also prevents the transfer of discharged electrons to the conductive layer.

Generally, the adhesive layer is located between the generating layer and the blocking layer and has a thickness of about 0.01 to about 2 microns. The adhesive layer is selected from several known adhesives, for example, PE-100, PE-200 and 49000 (EI du P
ont de Nemours & Company) or 4-polyvinylpyridine.

Also, if desired, the photoreceptor may include an overcoat. Suitable overcoatings can be used in making the photoreceptors of the present invention. Typical overcoatings include, for example, the silicone overcoat, Elvamido, disclosed in U.S. Pat. No. 4,565,760.
de) (available from EI du Pont de Nemours & Company), such as tin oxide particles dispersed in a binder, such as tin oxide particles disclosed in U.S. Pat. No. 4,426,435, e.g. Metallocene compounds in binders disclosed in U.S. Pat. No. 4,315,980, antimony-tin particles in binders, continuous binder phase disclosed in U.S. Pat. No. 4,515,882. There are charge transport molecules included with the charge injection particles, and polyurethane overcoating and the like.
U.S. Pat. Nos. 4,565,760 and 4,426,
No. 435, No. 4,315,980 and No. 4,515,
No. 882 is incorporated herein by reference. The choice of overcoating material is based on the specific photoreceptor manufactured and the desired protective and electrical properties. Generally, overcoating is
It has a thickness between about 0.5 microns and about 10 microns.

The coating material containing the film-forming polymer can be deposited on the imaging member from a solution, dispersion, emulsion or powder by any suitable technique. However, the deposited coating must form a thin, substantially uniformly flowable coating on the mandrel prior to solidification of the coating. Typical techniques for applying coatings include spray coating,
There are dip coating, wire wound rod coating, powder coating, electrostatic coating, sonic spray method, knife coating method and the like. If the coating is performed by a spray method, the spray method can be performed with or without gas. Spraying can be assisted by electrical means such as mechanical and / or electrostatic painting. Materials and method parameters are interdependent in the spray coating operation. Method parameters include atomizing gas pressure, solution flow rate, secondary gas nozzle pressure, atomizer to substrate distance, atomizer travel speed, and mandrel rotation speed. Material parameters include, for example, solvent mixtures that affect drying characteristics, dissolved solids concentration, dissolved solids (eg, monomer, polymer) composition, and dispersion when using dispersions and solutions. Solids concentration. The deposited coating is uniform, smooth and free of drawbacks such as air entrainment gas bubbles.

Specific embodiments of the present invention will be described below in detail. These examples are intended to illustrate in detail and do not limit the invention to the materials, conditions or parameters of these methods described in the embodiments. All parts and percentages are by weight unless otherwise specified.

[0057]

EXAMPLES Example 1 A seamless belt including a laminate of a poly (pyrrole) layer and a polyvinyl fluoride layer was manufactured as follows. An electrolyte containing 0.10 mol of LiClO ₄ in acetonitrile was prepared, and then the monomer pyrrole was added to the electrolyte to a concentration of 0.18 mol. The nickel foil electrode cut from the seamless nickel mandrel was washed by immersing it in dilute sulfuric acid (about 0.1 mol) for 5 minutes, taken out of the dilute sulfuric acid, rinsed first with water and then with ethanol, and dried the electrode. The electrochemical current of poly (pyrrole) was then applied onto the nickel foil electrode by a current / voltage source, a three-electrode potentiostat having a nickel working electrode and a sodium saturated calomel (SSCE) reference electrode, and a nickel auxiliary electrode. Adhesion was performed. With this potentiostat,
This makes it possible to apply a sufficiently limited potential difference between the working electrode and the reference electrode regardless of the magnitude of the current flow.
Electrode deposition was performed by applying a voltage of 0.76 V to SSCE and applying
Milliamp (mA) current was applied for 2-3 minutes until a uniform dark (black) coating of poly (pyrrole) was observed. The thickness of this poly (pyrrole) layer was about 2000 angstroms. Subsequently, washing was performed using CH ₃ CN, H ₂ O, and ethanol to remove LiClO ₄ . Using a low voltage alternating current (DC) power supply, polyvinyl fluoride was
DC, 1.2 mA, deposited on this electrode for 65 seconds, then coalesced at 180 ° C. for 5 minutes in a closed vessel and at 180 ° C. for 10 minutes in an open vessel, poly (pyrrole) / polyvinyl fluoride laminate I got This polyvinyl fluoride layer was about 3 mils thick. The resistivity of the belt surface in contact with the electrodes was 30-80 KΩ as measured by a high impedance digital multimeter (DDM) equipped with 2.54 cm (1 inch) spaced probes. This resistivity corresponds to a conductivity of about 0.1 to about 1.7 S / cm (Siemens / cm or Mo / cm). The conductivity on the opposite side was too low to measure. 35
The absorption spectrum of this film between 0 nm and 800 nm was relatively flat, showing panchromaticity and substantial transparency with an average value of 0.65 (20% transmission).

Example 2 A seamless belt including a laminate of a poly (pyrrole) layer and a polyvinyl fluoride layer was manufactured as follows. An electrolyte containing 0.102 mol of LiClO ₄ in acetonitrile was prepared, and then the monomer pyrrole was added to the electrolyte to a concentration of 0.25 mol. An electrode consisting of an electroformed nickel sleeve mandrel having a diameter of 8.4 cm (3.3 inches), a length of 7.6 cm (3 inches) and an inner surface area of 198 cm ² was first polished with 600 grit paper, followed by polishing the inner surface. 0
A mirror-finished surface was obtained by polishing using 00 steel wool, 3 micron diamond paste, 1 micron diamond paste and 0.25 micron diamond paste. The counter electrode was a concentric cylindrical nickel electrode having a smaller diameter than the working electrode. Then, electrochemical deposition of poly (pyrrole) was performed on the nickel electrode using a three-electrode potentiostat, a current / voltage source, and a sodium saturated calomel (SSCE) reference electrode. Table 1 shows the applied potential, steady state current, total anode charge, and polymerization time used to produce the conductive polymer layers of the five belts of the present invention. Poly (pyrrole) was deposited only on the inner surface of the nickel sleeve. By varying the total anode charge and the applied potential, various thicknesses of poly (pyrrole) layers were deposited. Subsequently, washing was performed using CH ₃ CN, H ₂ O, and ethanol to remove LiClO ₄ . Using a low voltage alternating current (DC) power supply, polyvinyl fluoride was
DC, 1.2 mA, deposited on this working electrode for 1 minute, then coalesced at 180 ° C. for 5 minutes in a closed vessel, 180 ° C. for 10 minutes in an open vessel, poly (pyrrole) / polyvinyl fluoride I got a seamless belt.
Minimum thickness is ground plane utilization
With sufficient surface conductivity for Although the absolute value of this thickness is not known, the visible absorbance of the laminate has been found to be a useful measure of thickness. The absorbance values shown in Table 1 are between 350 and 800
represents the average absorbance between nm and throughout this range,
The absorption spectrum was relatively constant. Therefore,
A maximum transmission of 20-22% is associated with a minimum value of conductivity sufficient for ground plane utilization. All laminates shown in Table 1 have excellent homogeneity in optical transmission over a large area, and according to visible observation measurements,
It exhibited low optical scattering properties and was all conductive on the outer surface. Q indicates the amount of electricity expressed in coulombs, and the deposition time in seconds is a function of the amount of electricity expressed in coulombs and the current expressed in amps. T (second) = Q (coulomb) / i (ampere)

Thus, for samples II-A through II-E, the adhesion times were 190 seconds, 210 seconds,
200 seconds, 200 seconds and 200 seconds. II-C, II
-D and II-E, these three
Certain laminates are highly resistant and are not desirable for ground plane applications. Because, in the imaging member, the current must flow through this layer,
High resistance indicates that the poly (pyrrole) layer of these laminates is too thin. The relatively small thickness of the poly (pyrrole) layers obtained for samples II-C, II-D and II-E is attributable to the low amount of electricity (10 coulombs) applied during deposition of these layers. can do. This is because the thickness of the obtained layer is proportional to the amount of electricity applied.

[0060]

[Table 1]

Example 3 A double-layer laminate of a poly (pyrrole) layer and a polyvinyl fluoride layer was produced as follows. 0.92 mol NaClO in acetonitrile
_An electrolyte containing ₄ was prepared, and then the monomer pyrrole was added to the electrolyte to a concentration of 0.25 molar. 8.4 cm (3.3 inches) in diameter, 7.6 cm (3 in) long
30% by weight of an electrode consisting of an electroformed nickel sleeve mandrel with an internal surface area of 198 cm ²
Was immersed in a bath consisting of a 1: 1 mixture of an aqueous hydrogen peroxide solution and a 30% aqueous ammonium hydroxide solution for about 1/2 hour. The counter electrode was a concentric cylindrical nickel electrode having a smaller diameter than the working electrode. Then, electrochemical deposition of poly (pyrrole) was performed on the nickel electrode using a three-electrode potentiostat, a current / voltage source, and a sodium saturated calomel (SSCE) reference electrode. The applied voltage was about 0.80 V with respect to SSCE in about 2.5 minutes. Subsequently, the substrate was washed with CH ₃ CN and ethanol to remove NaClO ₄ from the poly (pyrrole) layer, thereby obtaining a poly (pyrrole) layer having a thickness of about 1000 Å.

Next, a polymer suspension was prepared by electrophoretically depositing polyvinyl fluoride in a propylene carbonate / methanol solution (57/10 volume / volume) at a solid concentration of about 33% by volume. The deposition was performed on the working electrode (cathode) at -24 V at a range of 30-70 mA for about 6 minutes to obtain a uniform coating of uncured polymer on the electrode surface. Then, this polyvinyl fluoride,
5 minutes at 180 ° C in a closed container, 1
Combine at 80 ° C for 10 minutes, translucent poly (pyrrole)
/ A polyvinyl fluoride seamless belt was obtained. The seamless belt has a polyvinyl fluoride layer about 3 mils thick, the outer surface of the belt is conductive,
It exhibited a conductivity of about 6.8 × 10 ⁴ Ω / □, and the inner surface of the belt was non-conductive and exhibited an unmeasurable high resistance (> 20 MΩ / □). Visible-near infrared (I)
The R) spectrum showed that this material had sufficient panchromatic properties in an imaging member sensitive to visible or infrared light to make it suitable as an electrophotographic ground plane.

Example 4 A double layer laminate of a poly (pyrrole) layer and a polyvinylidene fluoride layer was prepared as follows. A layer of poly (pyrrole) was electrochemically deposited on the working electrode by the method described in Example 3.
A polyvinylidene fluoride was then prepared from a polymer suspension at a solids concentration of about 15% by weight in a propylene carbonate / methanol solution (57/10 v / v).
Electrophoresis adhered. The adhesion was +9 at the working electrode (anode).
This was performed at 0 V, about 4 mA for about 4 minutes to obtain a uniform coating of uncured polymer on the electrode surface. Subsequently, the polyvinylidene fluoride was heated at about 180 ° C. for about 2 hours.
Coalescing by heating for 0 minutes, 5 × 10 ⁴ Ω / □
A translucent poly (pyrrole) / polyvinylidene fluoride seamless belt having a conductive outer surface having a conductivity of The thickness of the poly (pyrrole) layer is about 500
0 Å and the thickness of the polyvinylidene fluoride layer was about 4 mils. The belt was cut open and tested by electrically grounding the poly (pyrrole) side and corona charging the surface of polyvinylidene fluoride. The surface voltage of this surface was measured within one second after charging. The belt was charged to a corona charge density of 1100 V and about 3.8 × 10 ⁻⁹ coulomb / cm ² . The surface voltage density decreases slowly after charging (40 V / sec).
Below). The charge-voltage data indicates that the double layer laminate is suitable as a particle radiographic image receiving substrate.

Example 5 A double layer laminate of a poly (pyrrole) layer and a poly (amide-imide) layer was produced as follows. A layer of poly (pyrrole) was electrochemically deposited on the working electrode by the method described in Example 3.
Then, a poly (amide-imide) (trade name: Torlon 4000T)
F, Amoco) was electrophoretically deposited from this polymer suspension. The suspension comprises about 1.01 g of the polymer in 1
It was prepared by slowly adding a solution of room temperature (about 25 ° C.) dissolved in 100 ml of methyl-2-pyrrolidinone to 300 ml of CH ₃ CN at 55 ° C. with vigorous stirring. The adhesion is + on the working electrode (anode).
20 V, about 2.0 mA for 12 minutes, then +40
V, about 4 mA for 38 minutes to obtain a uniform coating of uncured polymer on the electrode surface. Subsequently, the poly (amide-imide) is air-dried for about 10 minutes, the electrode is heated at about 110 ° C. for 80 minutes, and has a conductive outer surface having a conductivity of 3 × 10 ⁵ Ω / □, half A transparent poly (pyrrole) / poly (amide-imide) seamless belt was obtained. The thickness of the poly (pyrrole) layer was about 2000 angstroms and the thickness of the poly (amide-imide) layer was about 3 mils. The visible-near infrared spectrum of the laminate indicated that the material had sufficient panchromatic properties in an imaging member sensitive to visible or infrared light to be suitable as an electrophotographic ground plane.

Example 6 An electrophotographic imaging member was prepared by slitting the seamless belt prepared by the method of Example 3 and hand coating an additional layer on the conductive polymer surface in the following order. . A 0.8 mm thick blocking layer containing the methacrylate polymer was dissolved in Dowanol PM solvent (Dow Chemical) to a concentration of 8% and the solution was drawn through a draw bar with a 0.5 mil gap. And prepared by coating on a poly (pyrrole) surface. Then, poly (4
-Vinylpyridine) (Reilly Tar and Chemical Co.) was prepared by dissolving 0.12 g of this polymer in 17.9 g of isobutanol and 2 g of isopropanol and using a stretch bar with a 0.5 mil gap. Prepared by coating the surface of the blocking layer. 1 micron thick, 28.4% by weight trigonal selenium,
55.3% by weight of poly (N-vinylcarbazole) and N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl} -4,4′-diamine The photogenerating layer containing 3% by weight was composed of 8.57 g of trigonal selenium and 16.7 of poly (N-vinylcarbazole).
5 g and 4.93 g of the diamine are dissolved in 100.6 g of tetrahydrofuran and 100.6 g of toluene, and this solution is coated on a poly (4-vinylpyridine) surface using a drawing bar having a gap of 0.5 mil. Prepared. Finally, with a thickness of 25-30 microns,
N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl} -4,4'-diamine 40% by weight and bisphenol-A-polycarbonate (Makrolon (registered trademark)) Mobay Chemical Co.) 60
A charge transport layer comprising a mixture of 2% by weight of said diamine.
It was prepared by dissolving 8 g and 4.2 g of bisphenol-A-polycarbonate in 40 g of methylene chloride and coating this solution on a selenium surface using a drawing bar having a gap of 0.5 mil. The following table shows the electrical cycling behavior of this member when charged to a charge density of 140 nanocoulombs / cm ² by corona charging.
The surface potentials of all the members were measured with a capacitively-coupled voltage probe. The charge acceptance was measured 0.19 seconds after charging. The residual voltage was measured after exposing this member with a white light tungsten erasing lamp.

[0066]

[Table 2]

Excellent charge acceptance of about 1200 V and 40
Excellent residual voltage of ~ 50V was observed. These cycling characteristics are due to the absence of trapping in the bulk of each layer and each interface including the poly (pyrrole) / blocking layer interface. After standing for 24 hours, the member exhibited the following electrical properties.

[0068]

[Table 3]

As shown in the table, after standing for 24 hours, this member retained excellent electrical properties. These data indicate that the dual layer laminate of the present invention is desirable as a retentive support / base plane layer in an imaging member.

Example 7 US Pat. Nos. 4,524,371 and 4,463, the contents of which are incorporated herein by reference.
An electron acceptor suitable for particle radiographic imaging disclosed in US Pat. No. 363 was prepared by the method of Example 4. The electron acceptor has a double layer laminate including a poly (pyrrole) layer and a polyvinylidene fluoride layer,
Both layers were deposited on the outer surface of the working electrode, the counter electrode was concentric with the working electrode, the diameter was larger than the working electrode, and a seamless conductive belt with a conductive layer on the inner surface was obtained. Is the same as Example 4 except for. Next, the non-conductive polyvinylidene fluoride surface of the laminate was charged to 1200 V by corona discharge. afterwards,
It showed a dark decay of about 13.6 V / sec. Calculated by measuring the slope of the plot of voltage versus charge obtained with a grounded poly (pyrrole) layer,
When positively charged, the laminate exhibited a dielectric constant of about 18 to about 20, and when negatively charged, the laminate exhibited a dielectric constant of about 20 to about 24. These data indicate that the laminates of the present invention are suitable as imaging members for particle radiographic imaging applications.

While other embodiments and improvements of the present invention will occur to those skilled in the art from a consideration of the information herein, those embodiments and improvements and their equivalents will , Within the scope of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor William W. Lymberg, New York, United States of America 14526 Penfield Claireview Drive 66 (72) Inventor Santoque Es Badesha, United States of America 14534 Pittsford Bromley Road 48 (56) References JP 62-296152 (JP, A) JP-A-3-181477 (JP, A) JP-A-3-80256 (JP, A) JP-A-3-41462 (JP, A) JP-A-2-269360 (JP, A A) JP-A-62-106471 (JP, A) JP-A-55-133455 (JP, A) XEROX DISCLOSURE JOURNAL VOL. 14, NO. 2, MARCH / APRIL 1989, STAMFORD, CONN US PAGE93, "SEAMLESS COND UCTIVE SUBSTRATE FOR ELECTROTOPHOTOGRA PHIC APPLICATIONS"

Claims (2)

(57) [Claims] 1. An imaging member comprising a support and a photogenerating layer, wherein the support comprises a laminate of a conductive polymer layer and a host polymer layer comprising only a host polymer, wherein the surface of the conductive polymer layer is , ¹⁰ 2 ~10 ⁶ Ω / □
And the conductive polymer is poly (pyrrole), poly (alkylpyrrole), poly (2,5-
Thienylene), polyalkylthienylene, poly (2,
2'-bithiophene) and polyaniline. 2. A method of manufacturing an electrophotographic imaging member, comprising: a. A step of producing a seamless belt including a laminate of a conductive polymer layer and a host polymer layer composed of only a host polymer, comprising: (i) a non-aqueous solvent, an electrolyte, and a monomer which becomes a conductive polymer when polymerized. Preparing a solution: (ii) adding this solution to an electrolytic cell containing a working electrode, a counter electrode and a reference electrode; (iii) subjecting the anodic oxidation and polymerization of monomers to occur by applying a potential to the working electrode and the counter electrode. Conducting until a layer of conductive polymer material adheres to the working electrode; (iv) preparing a dispersion containing a liquid dispersion medium and a host polymer charged in the liquid dispersion medium; Adding the dispersion to an electrolytic cell including a working electrode having a polymer layer electrochemically attached thereto and a counter electrode: (vi) applying a potential to the working electrode and Performing electrophoretic deposition of the host polymer on the working electrode, which is caused by application to the counter electrode, until a layer of the host polymer is deposited on the conductive polymer present on the working electrode; (vii) subsequently, Heating the working electrode, thereby forming a two-layer laminate of the conductive polymer material and the host polymer; and (viii) separating the laminate from the electrode; and b. The above method, comprising the step of coating a layer of light generating material on the seamless belt.