JP2016186546A - Conductive roll, charging device, process cartridge, image forming apparatus, and manufacturing method of conductive roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive roll that has excellent accuracy in dimensions of an adhesive layer.SOLUTION: A conductive roll 121 comprises: a conductive base material 30; a conductive adhesive layer 33 that contains at least one of a polyimide resin and a polyimide resin precursor on the outer peripheral surface of the base material 30, where the total content of the polyimide resin and the polyimide resin precursor relative to the total resin and resin precursor is 50 mass% or more; and a conductive elastic layer 31 on the adhesive layer 33.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive roll, a charging device, a process cartridge, an image forming apparatus, and a method for manufacturing a conductive roll.

  In an image forming apparatus using an electrophotographic method, first, a laser beam that modulates an image signal by forming a charge on the surface of an image carrier made of a photoconductive photoreceptor containing an inorganic or organic material by using a charging device. After the electrostatic latent image is formed, the electrostatic latent image is developed with a charged toner to form a visualized toner image. Then, the toner image is electrostatically transferred to a transfer material such as recording paper via an intermediate transfer member or directly, and fixed on the recording material, whereby a reproduced image is obtained.

  Here, Patent Document 1 discloses a conductive roller provided with a conductive elastic layer on the outer periphery of a conductive support shaft, the conductive elastic layer having a rubber containing a halogen atom, and the conductive support shaft. And a conductive roller having a conductive adhesive layer having a phenol resin, an epoxy resin and a conductive agent between the conductive elastic layers, and a method for manufacturing the same.

  Further, Patent Document 2 discloses a method for producing a conductive roller having a conductive elastic layer around a core metal, the core metal having a predetermined length being used as a raw material composition for the conductive elastic layer. The mandrel that is continuously supplied to the crosshead connected to the extruder and passes through the crosshead and forms a coating of the raw material composition around the core metal, and then passes through the crosshead. A method of manufacturing a conductive roller is disclosed in which the coating covering the periphery of the core is cut into a predetermined length, and in the step, the traveling direction of the cored bar is vertically downward.

  Further, Patent Document 3 is an apparatus for manufacturing a rubber roll in which a core metal is covered with rubber, and a core metal supply unit that supplies a core metal having a positioning hole at the center of both end faces one by one, and the supplied core Supports a cored bar feeding part that feeds gold in series without gaps, a rubber coated part that coats rubber to the fed cored bar, and a roll that is pushed out from the rubber coated part while holding the roll straight. , Cut the coated rubber at the boundary between the preceding roll and the succeeding roll at a predetermined position, and detach only the preceding roll; receive and support the separated preceding roll; A manufacturing apparatus is disclosed that includes a rubber removal section on both ends that removes a covering rubber having a predetermined width to form a rubber roll.

  In Patent Document 4, in a rubber roller manufacturing method for coating a rubber material after applying a hot melt adhesive on the outer periphery of the core metal, the core metal coated with the adhesive is coated before the rubber material is coated. A method for producing a cooled rubber roller is disclosed.

JP 2006-208447 A Japanese Patent No. 4731914 Japanese Patent No. 3118639 JP 2006-334937 A

  The subject of this invention is providing the electroconductive roll excellent in the dimensional accuracy of an elastic layer compared with the case where an contact bonding layer contains only polyolefin-type resin as resin and a resin precursor.

The above problem is solved by the following means. That is,
The invention according to claim 1
A conductive substrate;
On the outer peripheral surface of the base material, at least one of a polyimide resin and a polyimide resin precursor is contained, and the total content of the polyimide resin and the polyimide resin precursor with respect to all the resins and resin precursors is 50% by mass or more. A conductive adhesive layer,
A conductive elastic layer on the adhesive layer;
A conductive roll having

The invention according to claim 2
The conductive roll according to claim 1, comprising a crosslinked polymer with an epoxy resin as at least one of the polyimide resin and the polyimide resin precursor.

The invention according to claim 3
The conductive roll according to claim 1 or 2, wherein the adhesive layer has a gel fraction of 50% or more.

The invention according to claim 4
The electroconductive roll as described in any one of Claims 1-3 is provided,
A charging device for charging the member to be charged by bringing the conductive roll into contact with the member to be charged.

The invention according to claim 5
An image carrier,
A charging device comprising the conductive roll according to any one of claims 1 to 3, and charging the image carrier by bringing the conductive roller into contact with the image carrier,
With
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 6
An image carrier,
A charging device comprising the conductive roll according to any one of claims 1 to 3, and charging the image carrier by bringing the conductive roller into contact with the image carrier,
A latent image forming apparatus for forming a latent image on the surface of the charged image carrier;
A developing device for developing a latent image formed on the surface of the image carrier with toner to form a toner image;
A transfer device for transferring the toner image formed on the surface of the image carrier to a recording medium;
An image forming apparatus comprising:

The invention according to claim 7 provides:
On the outer peripheral surface of the conductive base material, at least one of a polyimide resin and a polyimide resin precursor is contained, and the total content of the polyimide resin and the polyimide resin precursor with respect to all the resins and resin precursors is 50% by mass. An adhesive layer forming step of forming the conductive adhesive layer as described above;
Using an extrusion molding machine, the base material on which the adhesive layer is formed is supplied to the cross head while being inserted through a supply path having an inner diameter smaller than the outer diameter including the adhesive layer of the base material, and the cross head An elastic layer forming step of forming a conductive elastic layer by applying a material for forming an elastic layer on the adhesive layer,
The manufacturing method of the conductive roll which has this.

  According to the first aspect of the present invention, a conductive roll excellent in dimensional accuracy of the elastic layer is provided as compared with the case where the adhesive layer contains only a polyolefin resin as a resin and a resin precursor.

  According to invention of Claim 2, compared with the case where an adhesive layer contains only an uncrosslinked thing as a polyimide resin and a polyimide resin precursor, both peeling suppression of an adhesive layer and suppression of the film thickness nonuniformity of an elastic layer are compatible. A conductive roll is provided.

  According to the third aspect of the present invention, there is provided a conductive roll that is compatible with both suppression of peeling of the adhesive layer and suppression of film thickness unevenness of the elastic layer as compared with the case where the gel fraction of the adhesive layer is out of the above range. The

  According to invention of Claim 4, 5 and 6, compared with the case where an adhesive layer is provided with the conductive roll which contains only polyolefin resin as resin and resin precursor, generation | occurrence | production of the charging nonuniformity was suppressed. A process cartridge and an image forming apparatus are provided.

  According to invention of Claim 7, the manufacturing method of the electroconductive roll excellent in the dimensional accuracy of an elastic layer compared with the case where the contact bonding layer which contains only polyolefin resin as resin and resin precursor is formed is provided. The

It is a schematic perspective view which shows the electroconductive roll which concerns on this embodiment. It is a schematic sectional drawing of the electroconductive roll which concerns on this embodiment. It is the schematic which shows the extrusion molding machine provided with the crosshead. 1 is a schematic perspective view of a charging device according to an embodiment. 1 is a schematic configuration diagram illustrating an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows the process cartridge which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail.

[Conductive roll and manufacturing method thereof]
The conductive roll according to this embodiment includes a conductive base material, a conductive adhesive layer on the outer peripheral surface of the base material, and a conductive elastic layer on the adhesive layer. The adhesive layer contains at least one of a polyimide resin and a polyimide resin precursor, and the total content of the polyimide resin and the polyimide resin precursor with respect to all the resins and resin precursors included in the adhesive layer. Is 50 mass% or more.

Hereinafter, the polyimide resin and the polyimide resin precursor are collectively referred to as “polyimide material”.
With respect to all the resins and resin precursors contained in the adhesive layer, the polyimide material (polyimide resin and polyimide resin precursor) is contained in the adhesive layer as a main component (50% by mass or more). Here, the content of the polyimide-based material includes only the polyimide-based material and does not include the amount of the crosslinking agent in the case of a crosslinked polymer that is crosslinked by a crosslinking agent such as an epoxy resin described later.

A conductive roll having an adhesive layer and an elastic layer on the outer peripheral surface of the substrate is manufactured through a step of forming an adhesive layer on the substrate and a step of forming an elastic layer on the adhesive layer. For forming the elastic layer on the adhesive layer, a molding method such as an extrusion method using a crosshead or an injection molding method is used. Generally, the material for forming the elastic layer is heated. A method of applying on the adhesive layer is used.
However, when the elastic layer is formed as described above, thickness irregularities or irregularities may occur in the elastic layer, that is, the dimensional accuracy of the elastic layer may be inferior. Note that when a conductive roll having an elastic layer with uneven thickness and irregularities and inferior dimensional accuracy is applied to an image forming apparatus, image defects such as density unevenness and color points may occur in the formed image. It was.

  This is not necessarily clear, but the adhesive in the adhesive layer melts due to the heat applied to the elastic layer forming material, and the slipping property with the elastic layer forming material decreases, causing the adhesive layer to deform. It is presumed that thickness irregularities and irregularities are generated in the elastic layer.

On the other hand, in this embodiment, the adhesive layer is composed of a polyimide-based material (at least one of a polyimide resin and a polyimide resin precursor) as a main component (at least 50% by mass with respect to all the resins and resin precursors included in the adhesive layer). ). Thereby, unevenness in the thickness of the elastic layer and generation of irregularities are suppressed, that is, excellent dimensional accuracy of the elastic layer is realized. As a result, even when this conductive roll is applied to an image forming apparatus, the occurrence of image defects such as density unevenness and color points in the formed image is reduced.
This is because even when a material for forming an elastic layer is applied on the adhesive layer in a heated state, melting of the resin and resin precursor contained in the adhesive layer as an adhesive is suppressed, and the elastic layer forming material is formed. It is presumed that the slippage with the material is obtained, so that the deformation of the adhesive layer is suppressed, and the occurrence of uneven thickness and unevenness in the elastic layer is reduced.

-Crosslinked polymer with an epoxy resin In this embodiment, it is preferable to include a crosslinked polymer with an epoxy resin as a polyimide material (polyimide resin and polyimide resin precursor) contained in the adhesive layer. That is, it is preferable to include at least one of a crosslinked polymer of a polyimide resin and an epoxy resin and a crosslinked polymer of a polyimide resin precursor and an epoxy resin.

In the production of conductive rolls, as a method of forming an elastic layer on a base material, the base material previously coated with an adhesive is included in a molding apparatus such as an extruder equipped with a crosshead, including the adhesive layer of the base material. Further, there is an extrusion molding method in which the material is extruded together with a material for forming an elastic layer while being inserted through a supply path having an inner diameter smaller than the outer diameter.
However, when the base material and the elastic layer forming material are extruded and pass through the supply path, the cylindrical base material deviates from the center of the supply path, and therefore the thickness of the elastic layer is reduced. Different film thickness unevenness (uneven thickness) may occur depending on the location. Since unevenness in thickness (uneven thickness) leads to unevenness in conductivity, when a conductive roll having this unevenness in thickness (uneven thickness) is used in an image forming apparatus, image defects such as density unevenness may occur. It was.
In addition, in order to suppress the misalignment, a method of narrowing the width of the supply path for supplying the substrate to the crosshead is also conceivable. However, in this case, the adhesive layer formed on the outer peripheral surface of the substrate interferes. In some cases, the adhesive layer peeled off.

  On the other hand, by including a cross-linked polymer with an epoxy resin as a polyimide-based material contained in the adhesive layer, the adhesive layer is gelled and toughened. Therefore, when supplying the substrate having the adhesive layer from the supply path in the extrusion molding machine, it is allowed to pass through the supply path having a diameter smaller than the outer diameter of the substrate having the adhesive layer (the outer diameter including the adhesive layer), Backlash due to the supply path and the substrate is suppressed. As a result, it is presumed that the misalignment is suppressed and the occurrence of uneven thickness (uneven thickness) of the elastic layer is suppressed.

-Gel fraction of the adhesive layer The gel fraction of the adhesive layer is preferably 50% or more, more preferably 60% or more, and still more preferably 90% or more. By setting the gel fraction of the adhesive layer to 50% or more, the adhesive layer is strengthened and mechanical properties are improved. Therefore, when the substrate having the adhesive layer is supplied from the supply path in the extruder, the adhesive layer It is allowed to pass through a supply path having a diameter smaller than the outer diameter of the substrate having the outer diameter (the outer diameter including the adhesive layer). As a result, the occurrence of uneven thickness (uneven thickness) in the elastic layer is suppressed.

  The gel fraction of the adhesive layer may be controlled by changing the amount of crosslinking by adjusting the material of the adhesive used for the adhesive layer, the heating temperature at the time of forming the adhesive layer, the heating time, and the like. It is more preferable to adjust the gel fraction by adding an epoxy resin to the polyimide-based material and using both as a crosslinked polymer.

The gel fraction of the adhesive layer is measured according to JIS-K6796 (1998). Cut out 1 part by mass of the adhesive layer of the conductive roll and measure the mass. This is the mass of the resin before solvent extraction. After dissolving in solvent toluene (10 parts by mass) and soaking for 24 hours, the residual resin film is removed by filtration and the mass is measured. Let this mass be the mass after extraction. From these, the gel fraction is calculated according to the following formula.
Gel fraction (%) = ((mass after extraction) / (mass of resin before solvent extraction)) × 100
When the gel fraction is 50% or more, the coating film has a considerably developed cross-linked structure, and the crack resistance is good.

  In addition, as a manufacturing method of the electroconductive roll which concerns on this embodiment, it contains at least one of a polyimide resin and a polyimide resin precursor on the outer peripheral surface of an electroconductive base material, The said polyimide with respect to all the resins and resin precursors An adhesive layer forming step for forming a conductive adhesive layer having a total content of resin and the polyimide resin precursor of 50% by mass or more, and using an extrusion molding machine, the base material on which the adhesive layer is formed, The material is supplied to the crosshead while being inserted through a supply path having an inner diameter smaller than the outer diameter including the adhesive layer of the base material, and a material for forming an elastic layer is imparted on the adhesive layer from the crosshead to be conductive. It is preferable that it is a manufacturing method which has an elastic layer formation process which forms the elastic layer of this.

-Conductive roll-
First, the structure of a conductive roll is demonstrated using figures.

  FIG. 1 is a schematic perspective view showing an example of a conductive roll according to the present embodiment. 2 is a schematic cross-sectional view of the conductive roll shown in FIG. 1, and FIG. 2 is a cross-sectional view taken along line AA of FIG.

  As shown in FIGS. 1 and 2, the conductive roll 121 according to this embodiment includes, for example, a cylindrical or columnar substrate 30 (shaft) and an adhesive layer 33 disposed on the outer peripheral surface of the substrate 30. And a conductive elastic layer 31 disposed on the outer peripheral surface of the adhesive layer 33. Moreover, you may have the electroconductive outermost layer 32 arrange | positioned by the outer peripheral surface of the electroconductive elastic layer 31. FIG.

  In addition, the conductive roll 121 according to the present embodiment is not limited to the above-described configuration. For example, a resistance adjustment layer, a transition prevention layer, or a conductive layer disposed between the conductive elastic layer 31 and the conductive outermost layer 32. The structure which provided the coating layer (protective layer) arrange | positioned on the outer side (outermost surface) of the outermost layer 32 may be sufficient.

In this specification, the term “conductive” means that the volume resistivity at 20 ° C. is less than 1 × 10 ¹³ Ωcm.

  Hereinafter, the manufacturing method of the conductive roll and the conductive roll will be described separately for each step of the manufacturing method.

-Adhesive layer forming process-
(Base material)
The substrate 30 will be described.
As the base material 30, for example, a metal or alloy such as aluminum, copper alloy, or stainless steel; iron plated with chromium, nickel, or the like; a material made of a conductive material such as a conductive resin is used. It is done.

  The base material 30 functions as an electrode of a conductive roll and a support member. Examples of the material include metals such as iron (free-cutting steel, etc.), copper, brass, stainless steel, aluminum, nickel, and the like. In the present embodiment, the base material 30 is a conductive rod-like member. As the base material 30, a member (for example, a resin or a ceramic member) whose outer peripheral surface is plated, or a member in which a conductive agent is dispersed is used. (For example, resin and ceramic members) and the like are also included. The substrate 30 may be a hollow member (tubular member) or a non-hollow member.

(Adhesive layer)
The adhesive layer is a layer that adheres the conductive elastic layer 31 and the substrate 30.
The adhesive layer contains at least one of a polyimide resin and a polyimide resin precursor. That is, the polyimide resin precursor may be included in a state where it is not imidized, or may be included in a state where it is imidized to become a polyimide resin.
The total content of the polyimide-based material (polyimide resin and polyimide resin precursor) is 50% by mass or more and 70% by mass or more with respect to all the resins and resin precursors contained in the adhesive layer. Preferably, it is 90 mass% or more.

<Polyimide material>
As the polyimide resin, a thermosetting resin is particularly preferable. In the thermosetting polyimide, an imide group is directly connected to an organic group in a molecular main chain, and this is a polymer having a repeating unit. Examples of the organic group include a phenyl group, a naphthyl group, and a diphenyl group. By using these organic groups, those having good mechanical properties (scratch resistance) can be obtained.
A polyamic acid oligomer is mentioned as a polyimide resin precursor, It is obtained by carrying out the polycondensation reaction in the organic polar solvent for the equivalent of organic acid dianhydride and organic diamine.

-Polyamic acid composition-
Next, the polyamic acid composition used as a material for forming the adhesive layer will be described.
The polyamic acid composition contains a polyamic acid oligomer, and may further contain other materials such as conductive particles, an epoxy resin, and an organic polar solvent.

-Preparation of polyamic acid oligomer solution A polyamic acid oligomer is obtained by, for example, polymerizing an organic acid dianhydride (such as tetracarboxylic dianhydride) and a diamine compound in an organic polar solvent. Under the present circumstances, the molar ratio in connection with reaction of organic acid dianhydride and a diamine compound does not necessarily need to be equimolar. This is because in the process of polymerizing the polyamic acid oligomer, the functional group involved in the polymerization reaction remains, so that the polymerization reaction takes place based on this functional group, and as a result, the dispersion stability during the polymerization is improved, and the conductive property is further increased. This is because the bond between the conductive particles and the resin becomes stronger.

  Here, the polyamic acid oligomer is preferably a polymer having 1 unit of tetracarboxylic dianhydride and 1 mol of diamine compound as one unit, and the number n of the units is 1 or more and 60 or less. When the number of units is 60 or less, in the production process of the conductive particle-containing polyamic acid composition and the formation process of the adhesive layer, the dispersibility of the conductive particles becomes good and aggregation of the conductive particles is suppressed. . The number of units is controlled by the reaction temperature during polymerization, and the molecular weight increases as the reaction temperature increases.

Moreover, it is preferable that the polystyrene conversion weight average molecular weights of the said polyamic acid oligomer are 500 or more and 20000 or less. When the molecular weight is in the above range, the dispersibility of the conductive particles is improved and the aggregation of the conductive particles is suppressed in the production process of the conductive particle-containing polyamic acid composition and the formation process of the adhesive layer. The molecular weight is controlled by the reaction temperature during polymerization, and the molecular weight increases as the reaction temperature is increased.
The weight average molecular weight of the polyamic acid oligomer is measured by gel permeation chromatography (GPC). As GPC, Tosoh Corporation make: HLS-8120GPC (column: TSK gel series) is mentioned. Moreover, THF (tetrahydrofuran) is used as an eluent. As experimental conditions, an experiment is performed using a sample concentration of 0.5 mass%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an RI detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

  Further, the weight average molecular weight of the polyamic acid oligomer is determined by high performance liquid chromatography (HPLC) under the above measurement conditions using the above GPC column. The molecular weight of this polyamic acid oligomer is combined with the molecular weight of 1 mol of organic acid dianhydride (tetracarboxylic dianhydride) and 1 mol of diamine compound as a raw material for constituting the polyamic acid oligomer, and the molecular weight is 1 unit. And the number n of units of the polyamic acid oligomer is determined by dividing the weight average molecular weight by the molecular weight of the one unit.

・ Organic acid dianhydride (tetracarboxylic dianhydride)
There is no restriction | limiting in particular as an organic acid dianhydride (tetracarboxylic dianhydride) used for manufacture of a polyamic acid oligomer, Both an aromatic type and an aliphatic type compound are used.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyl. Sulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′- Biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1 , 2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyl) Noxi) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like.

  Aliphatic tetracarboxylic dianhydrides include butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2 -Acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 2- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides, aliphatic or alicyclic tetracarboxylic dianhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; 1,3 , a, 4,5,9b-Hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro Aliphatic tetracarboxylic dianhydrides having an aromatic ring such as -8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione Etc.

  As tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride is preferable, and pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3, 3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride is more preferred.

  These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

-Diamine compound Next, the diamine compound used for manufacture of a polyamic acid oligomer will not be specifically limited if it is a diamine compound which has two amino groups in molecular structure.

For example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4 ′ -Diaminodiphenylsulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6 -Amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5- Diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenyl ether, 2,7-diaminofluore 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diamino Biphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-diamino-2,2 ′ -Bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4 -Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3'-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) Luolene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) ) Phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl and other aromatic diamines; diaminotetraphenylthiophene and other aromatic rings An aromatic diamine having two amino groups and a hetero atom other than the nitrogen atom of the amino group; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine , Nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 4- diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 ^2.7] - undecylenate range methyl-diamine, 4 And aliphatic diamines such as 4,4'-methylenebis (cyclohexylamine) and alicyclic diamines.

  As the diamine compound, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, and 4,4'-diaminodiphenyl sulfone are preferable.

  These diamine compounds may be used alone or in combination of two or more.

-Combination of tetracarboxylic dianhydride and diamine compound The polyamic acid oligomer preferably contains an aromatic tetracarboxylic dianhydride and an aromatic diamine from the viewpoint of the strength of the adhesive layer.

Organic polar solvent Examples of the organic polar solvent used in the polyamic acid oligomer production reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide. Solvent, acetamide solvent such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvent such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-, m-, Or phenol solvents such as p-cresol, xylenol, halogenated phenol, catechol, ether solvents such as tetrahydrofuran, dioxane, dioxolane, alcohol solvents such as methanol, ethanol, butanol, cellosol such as butyl cellosolve And the like, hexamethylphosphoramide, and γ-butyrolactone. These are preferably used alone or as a mixture, but further, aromatic hydrocarbons such as xylene and toluene may be used in combination. The solvent is not particularly limited as long as it dissolves polyamic acid and polyamic acid-polyimide copolymer.

-Solid content concentration at the time of polyamic acid oligomer polymerization The solid content concentration of the polyamic acid oligomer solution is not particularly defined, but is preferably 50% by mass or less. When the solid content concentration at the time of polymerization is 50% by mass or less, generation of insoluble parts of the raw material monomer is suppressed during the reaction, and the reaction proceeds favorably, with the result that the strength of the adhesive layer is improved.

-Polyamic acid oligomer polymerization temperature As reaction temperature at the time of polyamic acid oligomer polymerization, it is preferable that it is the range of 0 degreeC or more and 80 degrees C or less. When the reaction temperature is 0 ° C. or higher, the viscosity of the solution is reduced, and the reaction system is well stirred. In addition, when the reaction temperature is 80 ° C. or lower, the occurrence of an imidization reaction in parallel with the polymerization of the polyamic acid oligomer is suppressed, which is preferable in terms of reaction control.

  The polyamic acid oligomer may be included in the adhesive layer in a state where it is not imidized as it is, or may be included in a state where it is imidized to become a polyimide resin.

  It is preferable to further add conductive particles to the polyamic acid oligomer solution prepared by the above-described method and disperse it to prepare a coating solution for forming an adhesive layer.

-Conductive particles As the conductive particles, there is no particular limitation as long as a conductive or semiconductive powder is used and the required electrical resistance can be obtained. Examples thereof include carbon blacks such as ketjen black and acetylene black, metals such as aluminum and nickel, metal oxide compounds such as tin oxide, potassium titanate and the like. These may be used alone or in combination.
Among these, in view of dispersibility in resin and resin precursor, dispersion stability, variation in conductivity, electric field dependency, and stability of electrical resistance over time, oxidized carbon black having a pH of 5 or less is preferable. .

  Oxidized carbon black is produced by oxidizing carbon black to impart a carboxyl group, a quinone group, a lactone group, a hydroxyl group, or the like to the surface. The oxidation treatment is performed by an air oxidation method in which it is brought into contact with air and reacted, a method in which it reacts with nitrogen oxide or ozone, a method in which ozone is oxidized after air oxidation, or the like. Specifically, the oxidized carbon black can be manufactured by a contact method. Examples of the contact method include a channel method and a gas black method. The oxidized carbon black may be produced by a furnace black method using gas or oil as a raw material. After these treatments, a liquid phase oxidation treatment with nitric acid or the like may be performed. Acidic carbon black can be manufactured by a contact method, but is generally manufactured by a closed furnace method. In the furnace method, carbon black having a relatively high pH and a low volatile content is usually produced. However, the pH may be adjusted by performing the above-described liquid-phase acid treatment. For this reason, carbon black obtained by a furnace method and adjusted to have a pH of 5 or less by post-treatment can be used.

  The pH value of the oxidized carbon black is preferably pH 5.0 or less, more preferably pH 4.5 or less, and still more preferably pH 4.0 or less. Oxidized carbon having a pH of 5.0 or lower has an oxygen-containing functional group such as a carboxyl group, a hydroxyl group, a quinone group, and a lactone group on the surface, so that it has good dispersibility in the resin and good dispersion stability is obtained. Variations in conductivity are suppressed, electric field dependency is reduced, and electric field concentration due to transfer voltage is difficult to occur.

  Here, pH is calculated | required by preparing the aqueous suspension of carbon black and measuring with a glass electrode. Moreover, the pH of acidic carbon black can be adjusted with conditions, such as the process temperature in an oxidation treatment process, and process time.

  The oxidation-treated carbon black has a volatile component of preferably 1% by mass or more and 25% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and further preferably 3.5% by mass or more and 15% by mass or less. Is preferred. When the volatile content is 1% by mass or more, the effect of the oxygen-containing functional group attached to the surface is satisfactorily exhibited, and the dispersibility in the resin is improved. On the other hand, when it is 25% by mass or less, decomposition when dispersed in the binder resin is suppressed, and moisture adsorbed on the oxygen-containing functional groups on the surface is suppressed, and an adhesive layer having a good appearance is formed. . Therefore, the dispersion | distribution in binder resin becomes more favorable by making a volatile content into the said range. This volatile content is determined by the ratio of organic volatile components (carboxyl group, hydroxyl group, quinone group, lactone group, etc.) that come out when carbon black is heated at 950 ° C. for 7 minutes.

  Specific examples of the oxidized carbon black include “Printex 150T” (pH 4.5, volatile content 10.0% by mass) and “Special Black 350” (pH 3.5, volatile) manufactured by Orion Engineered Carbons. 2.2% by mass), “Special Black 100” (pH 3.3, volatile content 2.2% by mass), “Special Black 250” (pH 3.1, volatile content 2.0% by mass), “ Special Black 5 ”(pH 3.0, volatile content 15.0% by mass),“ Special Black 4 ”(pH 3.0, volatile content 14.0% by mass),“ Special Black 4A ”(pH 3.0, volatile) 14.0% by mass), “Special Black 550” (pH 2.8, volatile content 2.5% by mass), “Special Black 6” (pH 2.5, volatile content 18.0% by mass), “Color Black FW200” (pH 2.5, volatile content 20.0% by mass), “Color Black FW2” (pH 2.5, volatile content 16.5% by mass), “Color Black FW2V” (pH 2.5, Volatile content 16.5% by mass), Cabot “MONARCH1000” (pH 2.5, volatile content 9.5% by mass), Cabot “MONARCH 1300” (pH 2.5, volatile content 9.5% by mass), Cabot “MONARCH1400” (pH 2.5, volatile matter 9.0% by mass), “MOGUL-L” (pH 2.5, volatile matter 5.0% by mass), “REGAL400R” (pH 4.0, volatile matter) 3.5% by mass).

A known method is applied as the dispersion method, and examples thereof include a ball mill, a sand mill, a basket mill, and ultrasonic dispersion.
The polyamic acid oligomer is preferably 5 to 40 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the organic polar solvent.
The carbon black is preferably 2 parts by mass or more and 16 parts by mass, more preferably 2 parts by mass or more and 14 parts by mass or less, and still more preferably 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the organic polar solvent.

  Here, the mass of the polyamic acid oligomer is preferably 0.001% or more and 50% or less with respect to the sum of the masses of the tetracarboxylic dianhydride, the diamine compound, and the polyamic acid oligomer. Furthermore, when the unit number n of the polyamic acid oligomer is 1 or more and less than 30, or the mass average molecular weight of the polyamic acid oligomer is 500 or more and less than 5000, the mass of the polyamic acid oligomer is calculated from tetracarboxylic dianhydride, diamine compound, It is preferable that it is 0.001% or more and 30% or less with respect to the sum of the mass with a polyamic acid oligomer, On the other hand, the unit number n of a polyamic acid oligomer is 30 or more and 60 or less, or the mass average molecular weight of a polyamic acid oligomer is 5000 or more. In the case of 20000 or less, the mass of the polyamic acid oligomer is preferably 30% or more and 50% or less with respect to the sum of the masses of the tetracarboxylic dianhydride, the diamine compound, and the polyamic acid oligomer.

-Other resin In addition, you may use other resin other than a polyimide-type material together for a contact bonding layer. The material forming the adhesive layer preferably has heat resistance, and is not particularly limited as a heat-resistant resin material. For example, polyester, polyethylene terephthalate, polyethersulfone, polyetherketone, polysulfone, polyimide Examples include amides and polyamides. Among them, those classified as aromatic polyamide (aramid) and thermotropic liquid crystal polymer are preferable. Examples of the thermotropic liquid crystal polymer include fully aromatic polyester, aromatic-aliphatic polyester, aromatic polyazomethy, and aromatic polyester-carbonate.

-Crosslinked polymer with epoxy resin-
Moreover, it is preferable that a polyimide-type material is a crosslinked polymer with an epoxy resin.

The epoxy resin used for the adhesive layer of this embodiment is not particularly limited as long as it is a compound having two or more epoxy groups.
Epoxy resins include monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, biphenyl type epoxy resins, bisphenol type epoxy resins , Stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, phenol Examples thereof include aralkyl type epoxy resins (having a phenylene skeleton, a diphenylene skeleton, and the like), and these may be used alone or in combination.

  Among these, biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin are preferable, biphenyl type epoxy resin, bisphenol type epoxy resin, Phenol novolac type epoxy resins and cresol novolac type epoxy resins are more preferred, and bisphenol type epoxy resins are more preferred.

  As the epoxy resin, at least one selected from bisphenol A type epoxy resin and bisphenol F type epoxy resin, urethane-modified epoxy resin, and rubber-modified epoxy resin may be used in combination.

-Curing accelerator-
You may use a hardening accelerator for the contact bonding layer which concerns on this embodiment further. Examples of the curing accelerator include phosphate, tertiary amine, tertiary amine salt, imidazole, sulfonium salt and the like. Among these, phosphate is more preferable.

The phosphate is not particularly limited. For example, aluminum phosphate, aluminum metaphosphate, aluminum dipolyphosphate, titanium hydrogen phosphate, titanium pyrophosphate, zirconium hydrogen orthophosphate, cerium hydrogen orthophosphate, zinc phosphate, these are wet mixed with zinc oxide or magnesium oxide. And modified ones. Moreover, you may use what carried out the surface treatment of the phosphate at least one of Si and Zn. One preferred embodiment is that the phosphate has been subjected to a dehydration treatment. The phosphate is preferably finely pulverized from the viewpoint of redispersibility.
Of these, aluminum dihydrogen phosphate is preferred from the viewpoints of excellent adhesiveness, excellent dispersibility in the adhesive composition, and easy availability.

Tripolyaluminum dihydrogen phosphate is a compound represented by AlH ₂ P ₃ O ₁₀ . The trihydrogenaluminum dihydrogen phosphate is not particularly limited, and examples thereof include AlH ₂ P ₃ O ₁₀ and AlH ₂ P ₃ O ₁₀ · 2H ₂ O.
One preferred embodiment of the aluminum dihydrogen tripolyphosphate is to use a finely pulverized one. Finely pulverized aluminum dihydrogen phosphate is commercially available, and examples of these commercially available products include K-WHITE # 105 manufactured by Teika.

  The amount of the curing accelerator is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyimide-based material. In this range, the reactivity with the polyimide material, the dispersibility in the adhesive composition, and the water resistance are excellent.

-Epoxy resin curing agent-
The adhesive may contain a known curing agent. For example, what is used as a hardening | curing agent of an epoxy resin is mentioned.

Any epoxy resin curing agent known to those skilled in the art can be used. For example, straight chain aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine; metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diamino Aminos such as naphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide; resol type phenols such as aniline-modified resole resin and dimethyl ether resole resin Resin; phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, novolak type phenol resin such as nonylphenol novolak resin; polyoxystyrene such as polyparaoxystyrene; phenol resin such as phenol aralkyl resin; However, it is not particularly limited to these.
Two or more of these may be used in combination.

  Further, the content of the curing agent is not particularly limited, and the optimal amount varies depending on the type of the curing agent. For example, the conventionally known optimum amount for each curing agent is preferably used. This optimum amount is described, for example, in Chapter 3 of “Review Epoxy Resin Basics” (Epoxy Resin Technical Association, published in 2003).

・ Other components In addition to the above, the adhesive layer further comprises a catalyst, an inorganic filler, an organic or polymer filler, a flame retardant, an antistatic agent, a conductivity imparting agent, a lubricant, a slidability imparting agent, and a surface activity. An agent, a coloring agent, etc. may be contained. Two or more of these may be contained.

Furthermore, the adhesive forming the adhesive layer includes carbon black such as ketjen black and acetylene black for imparting conductivity; pyrolytic carbon, graphite; various conductive metals such as aluminum, copper, nickel, and stainless steel, Or conductive alloys such as tin oxide, indium oxide, titanium oxide, tin oxide antimony oxide solid solution, tin oxide indium oxide solid solution, etc .; It may be added.
The conductive powder added to the adhesive layer is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the adhesive layer.

-Formation of an adhesive layer In addition, an adhesive layer can be formed by apply | coating the coating liquid for adhesive layer formation on the said base material.
The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less.

-Conductive elastic layer formation process-
(Conductive elastic layer)
The conductive elastic layer 31 will be described.
The conductive elastic layer 31 includes, for example, an elastic material, a conductive agent, and other additives as necessary. And the conductive elastic layer 31 is a layer formed on the outer peripheral surface of the base material 30 through an adhesive layer.

  Elastic materials include isoprene rubber, chloroprene rubber, epichlorohydrin rubber, butyl rubber, polyurethane, silicone rubber, fluorine rubber, styrene-butadiene rubber, butadiene rubber, nitrile rubber, ethylene propylene rubber, epichlorohydrin-ethylene oxide copolymer rubber, epichlorohydrin-ethylene oxide- Examples include allyl glycidyl ether copolymer rubber, ethylene-propylene-diene terpolymer rubber (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), natural rubber, and blend rubbers thereof. Among these, polyurethane, silicone rubber, EPDM, epichlorohydrin-ethylene oxide copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer rubber, NBR and blended rubbers thereof are preferably used. These elastic materials may be foamed or non-foamed.

Examples of the conductive agent include an electronic conductive agent and an ionic conductive agent. Examples of the electronic conductive agent include carbon black such as ketjen black and acetylene black; pyrolytic carbon, graphite; various conductive metals or alloys such as aluminum, copper, nickel, stainless steel; tin oxide, indium oxide, titanium oxide And various conductive metal oxides such as tin oxide-antimony oxide solid solution and tin oxide-indium oxide solid solution; Examples of ionic conductive agents include perchlorates and chlorates such as tetraethylammonium and lauryltrimethylammonium; alkali metals such as lithium and magnesium; perchlorates and chlorates of alkaline earth metals ;
These conductive agents may be used alone or in combination of two or more.

The carbon black specifically includes “Special Black 350”, “Special Black 100”, “Special Black 250”, “Special Black 5”, and “Special Black” manufactured by Orion Engineered Carbons. 4 ”,“ Special Black 4A ”,“ Special Black 550 ”,“ Special Black 6 ”,“ Color Black FW200 ”,“ Color Black FW2 ”,“ Color Black FW2V ”,“ MONARCH1000 ”manufactured by Cabot Corporation ”,“ MONARCH1300 ”,“ MONARCH1400 ”,“ MOGUL-L ”,“ REGAL400R ”, and the like.
The average particle diameter of these conductive agents is preferably 1 nm or more and 200 nm or less.
The average particle diameter is calculated by using a sample cut out of the conductive elastic layer 31, observing with an electron microscope, measuring 100 diameters (maximum diameter) of the conductive agent, and averaging them. The average particle diameter may be measured using, for example, Zetasizer Nano ZS manufactured by Sysmex Corporation.

  The addition amount of the conductive agent is not particularly limited, but in the case of the electronic conductive agent, it is preferably in the range of 1 part by mass or more and 30 parts by mass or less, and 15 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of the elastic material. More preferably, it is in the range of less than or equal to parts by mass. On the other hand, in the case of the ionic conductive agent, it is preferably in the range of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the elastic material, and is 0.5 to 3.0 parts by mass. The following range is more preferable.

  Examples of other additives blended in the conductive elastic layer 31 include a softener, a plasticizer, a curing agent, a vulcanizing agent, a vulcanization accelerator, an antioxidant, a surfactant, a coupling agent, and a filler ( Examples thereof include materials that can be added to a normal elastic layer such as silica and calcium carbonate.

Formation of conductive elastic layer The conductive elastic layer 31 is formed by, for example, extruding a material for forming a conductive elastic layer together with the base material 30 on which the adhesive layer is formed, using an extrusion molding machine equipped with a crosshead or the like. By this, it is formed on the outer peripheral surface of the adhesive layer.

  Here, a method for forming a conductive elastic layer by an extruder equipped with a crosshead will be described with reference to the drawings.

  FIG. 3 shows a configuration of a rubber roll manufacturing apparatus (an extrusion molding machine equipped with a crosshead) 210 used for forming the elastic layer in the present embodiment.

  The rubber roll manufacturing apparatus 210 according to the present embodiment includes a discharger 212 constituted by a so-called cross head die, a pressurizer 214 disposed below the discharger 212, and a drawer 216 disposed below the pressurizer 214. And.

  The discharger 212 extrudes the rubber material supplied from the rubber material supply unit 218 into a cylindrical shape, and supplies the unvulcanized rubber material (the material for forming the conductive elastic layer 31 described above). An extrusion unit 220 and a cored bar supply unit 224 that supplies the cored bar 222 (the base material 30 on which the adhesive layer is formed) to the central part of the rubber material extruded from the extruded unit 220 in a cylindrical shape. .

  The rubber material supply unit 218 has a screw 228 inside a cylindrical main body 226. The screw 228 is rotationally driven by the drive motor 230. On the drive motor 230 side of the main body 226, a charging port 232 for charging a rubber material is provided. The rubber material introduced from the introduction port 232 is sent out toward the extrusion part 220 while being kneaded by the screw 228 inside the main body part 226. By adjusting the rotational speed of the screw 228, the speed at which the rubber material is fed out is adjusted.

  The extrusion unit 220 includes a cylindrical case 234 connected to the rubber material supply unit 218, a columnar mandrel 236 disposed at the center of the case 234, a discharge head 238 disposed below the mandrel 236, It has. The mandrel 236 is held by the case 234 by the holding member 240. The discharge head 238 is held in the case 234 by a holding member 242. Between the outer peripheral surface of the mandrel 236 (in part, the outer peripheral surface of the holding member 240) and the inner peripheral surface of the holding member 242 (in part, the inner peripheral surface of the discharge head 238), an annular flow in which the rubber material flows in an annular shape A path 244 is formed.

  An insertion hole 246 through which the core bar 222 is inserted is formed at the center of the mandrel 236. The lower part of the mandrel 236 has a tapered shape toward the end. A region below the tip of the mandrel 236 is a joining region 248 where the cored bar 222 supplied from the insertion hole 246 and the rubber material supplied from the annular channel 244 join together. That is, the rubber material is pushed out in a cylindrical shape toward the merge area 248, and the cored bar 222 is fed into the central portion of the rubber material pushed out in the cylindrical shape.

  The metal core supply unit 224 includes a roller pair 250 disposed above the mandrel 236. A plurality of roller pairs 250 (three pairs) are provided, and one roller of each roller pair 250 is connected to a driving roller 254 via a belt 252. When the driving roller 254 is driven, the cored bar 222 sandwiched between the roller pairs 250 is sent toward the insertion hole 246 of the mandrel 236. The core metal 222 has a predetermined length, and the rear core metal 222 sent by the roller pair 250 presses the front core metal 222 existing in the insertion hole 246 of the mandrel 236, whereby a plurality of core bars 222 are formed. Are sequentially passing through the insertion hole 246. Further, the driving of the driving roller 254 is temporarily stopped when the front end of the front cored bar 222 is positioned at the tip of the mandrel 236, and the cored bar 222 is fed at an interval in a confluence region 248 below the mandrel 236. It is.

  Thus, in the discharger 212, the rubber material is extruded into a cylindrical shape in the merging area 248, and the cored bar 222 is sequentially fed into the central portion of the rubber material with an interval. Accordingly, the outer peripheral surface of the cored bar 222 is covered with a rubber material, and the rubber roll portion 256 (that is, the above-described conductive elastic layer) is applied to the outer peripheral surface of the cored bar 222 (the base material 30 on which the above-described adhesive layer is formed). It is formed.

The thickness of the conductive elastic layer 31 is preferably 1 mm or more and 10 mm or less, and more preferably 2 mm or more and 5 mm or less.
The volume resistivity of the conductive elastic layer 31 is preferably 10 ³ Ωcm or more and 10 ¹⁴ Ωcm or less.

Application The conductive roll according to the present embodiment is used as a roll member that requires electrical continuity. For example, in an image forming apparatus, an image such as a charging roll or toner that contacts the member to be charged and charges the member to be charged. It is used as a transfer roll or the like for transferring an image forming material by directly contacting a holding body for holding the forming material or indirectly through another member and applying an electric charge to the image forming material.
Specifically, in an electrophotographic image forming apparatus, a charging roll for charging an image carrier (photoreceptor), and primary transfer for primarily transferring a toner image held on the image carrier (photoreceptor) to an intermediate transfer member. Roll, secondary transfer roll for secondary transfer of toner image held on intermediate transfer body to recording medium, transport of recording medium and toner image held on image holding body (photoreceptor) directly on recording medium And a transfer roller for transferring the toner image to the image forming member, a developing roller for developing the electrostatic latent image held on the image holding member (photosensitive member), and the like.

(Conductive outermost layer)
The polymer material constituting the conductive outermost layer 32 is not particularly limited, but polyamide, polyurethane, polyvinylidene fluoride, tetrafluoroethylene copolymer, polyester, polyimide, silicone resin, acrylic resin, polyvinyl butyral, ethylene tetra Fluoroethylene copolymer, melamine resin, fluororubber, epoxy resin, polycarbonate, polyvinyl alcohol, cellulose, polyvinylidene chloride, polyvinyl chloride, polyethylene, ethylene vinyl acetate copolymer and the like.
The above polymer materials may be used alone or in combination of two or more. Further, the number average molecular weight of the polymer material is preferably in the range of 1,000 or more and 100,000 or less, and more preferably in the range of 10,000 or more and 50,000 or less.

  The conductive outermost layer 32 may be formed of a composition obtained by mixing the above-described polymer material with the conductive agent used in the conductive elastic layer 31 as a conductive agent and various particles shown below. The addition amount is not particularly limited, but is preferably in the range of 1 to 50 parts by mass, preferably in the range of 5 to 20 parts by mass with respect to 100 parts by mass of the polymer material. More preferred.

  Examples of the particles include metal oxides such as silicon oxide, aluminum oxide, and barium titanate, and composite metal oxides, and polymer powders such as tetrafluoroethylene and vinylidene fluoride. It is not limited to.

The thickness of the conductive outermost layer 32 is preferably thick considering durability due to wear as a charging member, but is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.1 μm or more and 500 μm or less, and more preferably 0.5 μm or more. More preferably, it is 100 μm or less.
As a method for forming the conductive outermost layer 32, the conductive outermost layer 32 is formed on the conductive elastic layer by dipping, spraying, vacuum deposition, plasma coating, or the like. It is advantageous.

[Charging device]
Hereinafter, the charging device according to the present embodiment will be described.
FIG. 4 is a schematic perspective view of the charging device according to the present embodiment.

The charging device according to the present embodiment is a form in which the conductive roll according to the present embodiment is applied as the conductive roll.
Specifically, as illustrated in FIG. 4, for example, the charging device 12 according to the present embodiment is configured such that the conductive roll 121 and the cleaning member 122 are in contact with each other with a specific amount of biting. Then, both axial ends of the base material 30 of the conductive roll 121 and the base material 122A of the cleaning member 122 are held by a conductive bearing 123 (conductive bearing) so that each member can rotate. A power supply 124 is connected to one of the conductive bearings 123.
Note that the charging device according to the present embodiment is not limited to the above-described configuration, and may be a form that does not include the cleaning member 122, for example.

  The cleaning member 122 is a cleaning member for cleaning the surface of the conductive roll 121, and is configured in a roll shape, for example. The cleaning member 122 includes, for example, a cylindrical or columnar base material 122A, and an elastic layer 122B on the outer peripheral surface of the base material 122A.

  The base material 122A is a conductive rod-like member, and examples of the material thereof include metals such as iron (free-cutting steel and the like), copper, brass, stainless steel, aluminum, and nickel. Examples of the base material 122A include a member (for example, a resin or a ceramic member) whose outer peripheral surface is plated, a member in which a conductive agent is dispersed (for example, a resin or a ceramic member), and the like. The base material 122A may be a hollow member (cylindrical member) or a non-hollow member.

  The elastic layer 122B is made of a foam having a porous three-dimensional structure. The elastic layer 122B preferably has elasticity, with cavities and concavo-convex portions (hereinafter referred to as cells) inside and on the surface. The elastic layer 122B is made of polyurethane, polyethylene, polyamide, olefin, melamine or polypropylene, NBR (acrylonitrile-butadiene copolymer rubber), EPDM (ethylene-propylene-diene copolymer rubber), natural rubber, styrene butadiene rubber, chloroprene, silicone, It includes a foamable resin material such as nitrile or a rubber material.

  Among these foamable resin materials or rubber materials, foreign substances such as toner and external additives are efficiently cleaned by driven sliding friction with the conductive roll 121, and at the same time, the cleaning member 122 is formed on the surface of the conductive roll 121. In order to make it difficult to scratch due to rubbing, and to prevent tearing and breakage from occurring over a long period of time, polyurethane which is strong in tearing and tensile strength is particularly preferably applied.

  The polyurethane is not particularly limited. For example, polyol (for example, polyester polyol, polyether polyol, acrylic polyol, etc.) and isocyanate (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4, etc.) -Reaction products of diphenylmethane diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, etc.), and reaction products of these chain extenders (for example, 1,4-butanediol, trimethylolpropane, etc.) may be used. . Polyurethane is generally foamed using a foaming agent (water or an azo compound (azodicarbonamide, azobisisobutyronitrile, etc.).

  The number of cells of the elastic layer 122B is preferably 20/25 mm or more and 80/25 mm or less, more preferably 30/25 mm or more and 80/25 mm or less, and 30/25 mm or more and 50/25 mm or less. Particularly preferred.

  The hardness of the elastic layer 122B is preferably 100N to 500N, more preferably 100N to 400N, and particularly preferably 150N to 400N.

  The conductive bearing 123 is a member that holds the conductive roll 121 and the cleaning member 122 integrally and rotatably, and also holds an interaxial distance between the members. The conductive bearing 123 may be of any material and form as long as it is made of a conductive material. For example, a conductive bearing or a conductive sliding bearing is applied.

  The power supply 124 is a device that charges the conductive roll 121 and the cleaning member 122 to the same polarity by applying a voltage to the conductive bearing 123, and a known high-voltage power supply device is used.

  In the charging device 12 according to this embodiment, for example, when a voltage is applied from the power source 124 to the conductive bearing 123, the conductive roll 121 and the cleaning member 122 are charged with the same polarity.

[Image forming apparatus, process cartridge]
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, a latent image forming unit that forms a latent image on the surface of the charged image carrier, and a surface of the image carrier. Developing means for developing the formed latent image with toner to form a toner image, and transfer means for transferring the toner image formed on the surface of the image carrier to a recording medium. The charging device according to the present embodiment is applied as the charging means (charging device).

  On the other hand, the process cartridge according to this embodiment includes, for example, an image holding member that is detached from the image forming apparatus having the above-described configuration, and a charging unit that charges the image holding member. The charging device according to the present embodiment is applied as the charging unit. The process cartridge according to the present embodiment includes, as necessary, developing means for developing a latent image formed on the surface of the image carrier with toner to form a toner image, and a toner image formed on the surface of the image carrier. At least one selected from the group consisting of a transfer unit that transfers the toner to a recording medium and a cleaning unit that removes residual toner on the surface of the image carrier after transfer.

  Next, an image forming apparatus and a process cartridge according to the present embodiment will be described with reference to the drawings. FIG. 5 is a schematic configuration diagram illustrating the image forming apparatus according to the present embodiment. FIG. 6 is a schematic configuration diagram showing a process cartridge according to the present embodiment.

  As shown in FIG. 5, the image forming apparatus 101 according to the present embodiment includes an image carrier 10, a charging device 12 that charges the image carrier around the image carrier 10, and an image carrier charged by the charging device 12. An exposure device 14 that exposes 10 to form a latent image, a developing device 16 that develops the latent image formed by the exposure device 14 with toner to form a toner image, and a toner image that is formed by the developing device 16 A transfer device 18 for transferring to P and a cleaning device 20 for removing residual toner on the surface of the image carrier 10 after transfer are provided. Further, a fixing device 22 for fixing the toner image transferred to the recording medium P by the transfer device 18 is provided.

  The image forming apparatus 101 according to the present embodiment includes, as the charging device 12, for example, a conductive roll 121, a cleaning member 122 disposed in contact with the conductive roll 121, and shafts of the conductive roll 121 and the cleaning member 122. In the present embodiment, a conductive bearing 123 (conductive bearing) that holds both ends of the direction so that each member can rotate and a power source 124 connected to one of the conductive bearings 123 are disposed. Such a charging device is applied.

  On the other hand, in the image forming apparatus 101 of the present embodiment, a known configuration is conventionally applied as each configuration of the electrophotographic image forming apparatus, except for the charging device 12 (conductive roll 121). Hereinafter, an example of each configuration will be described.

  The image carrier 10 is not particularly limited, and a known photoreceptor can be used. An organic photoreceptor having a so-called function separation type structure in which a charge generation layer and a charge transport layer are separated is preferably used. Further, the image carrier 10 whose surface layer is covered with a protective layer having a charge transporting property and having a crosslinked structure is also suitably applied. A photoreceptor composed of a siloxane-based resin, a phenol-based resin, a melamine resin, a guanamine resin, or an acrylic resin as a crosslinking component of the protective layer is also suitably applied.

  As the exposure device 14, for example, a laser optical system, an LED array, or the like is applied.

  For example, the developing device 16 brings a toner image onto the latent image on the surface of the image carrier 10 by bringing a developer carrier having a developer layer formed on the surface thereof into contact with or close to the image carrier 10. A developing device to be formed. As a developing method of the developing device 16, a developing method using a two-component developer is suitably applied as a known method. Examples of the developing method using the two-component developer include a cascade method and a magnetic brush method.

  As the transfer device 18, for example, either a non-contact transfer method such as corotron or a contact transfer method in which a conductive transfer roll is brought into contact with the image carrier 10 via the recording medium P to transfer a toner image to the recording medium P. May be adapted.

  The cleaning device 20 is, for example, a member that removes toner, paper dust, dust, and the like adhering to the surface by bringing a cleaning blade into direct contact with the surface of the image carrier 10. As the cleaning device 20, a cleaning brush, a cleaning roll, or the like may be applied in addition to the cleaning blade.

  As the fixing device 22, a heat fixing device using a heat roll is suitably applied. The heat fixing device includes, for example, a fixing roller having a heater lamp for heating inside a cylindrical metal core, and a so-called release layer formed on the outer peripheral surface by a heat resistant resin coating layer or a heat resistant rubber coating layer; A pressure roller or a pressure belt that is disposed in contact with the fixing roller at a specific contact pressure and has a heat-resistant elastic body layer formed on the outer peripheral surface of the cylindrical core metal or the surface of the belt-like base material. . The fixing process of the unfixed toner image is performed, for example, by inserting the recording medium P on which the unfixed toner image is transferred between the fixing roller and the pressure roller or the pressure belt, and binding resin in the toner, Fixing by heat melting of additives and the like.

  The image forming apparatus 101 according to the present embodiment is not limited to the above configuration. For example, an intermediate transfer type image forming apparatus using an intermediate transfer member and an image forming unit that forms toner images of each color are arranged in parallel. A so-called tandem image forming apparatus may be used.

  On the other hand, as shown in FIG. 6, the process cartridge according to the present embodiment includes an opening 24A for exposure, an opening 24B for static elimination exposure, and a mounting rail 24C in the image forming apparatus shown in FIG. By the housing 24, the image carrier 10, the charging device 12 for charging the image carrier, the developing device 16 for developing the latent image formed by the exposure device 14 with toner and forming a toner image, and after the transfer And a cleaning device 20 that removes residual toner on the surface of the image holding body 10 and is integrally assembled and held. The process cartridge 102 is detachably attached to the image forming apparatus 101 shown in FIG.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited by the following Example. Unless otherwise specified, “part” means “part by mass”.

[Example 1]
<Preparation of conductive roll>
-Preparation of base material After applying the electroless nickel plating of 5 micrometers in thickness to the cylindrical base material which consists of SUM23L, hexavalent chromic acid was given and the electroconductive base material of diameter 8mm was obtained.

-Formation of adhesive layer (Preparation of polyamic acid oligomer solution (A-1))
Into a flask equipped with a stirrer, a thermometer and a dropping funnel, nitrogen gas dried with phosphorus pentoxide was passed through 29.42 g (0.1 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. ) And 117.68 g of N-methyl-2-pyrrolidone were injected, stirred and dissolved. Thereafter, a diamine solution prepared by dissolving 20.02 g (0.1 mol) of 4,4′-diaminodiphenyl ether in 80.08 g of N-methyl-2-pyrrolidone was dropped into a flask maintained at 0 ° C. Immediately after the dropping, the reaction solution was poured into a large amount of methanol (amount capable of reprecipitation purification) to perform reprecipitation purification. The precipitated white polymer was filtered off and dried, and then redissolved in N-methyl-2-pyrrolidone to obtain a 20% by mass polyamic acid oligomer solution (A-1).

  About the obtained polyamic acid oligomer, when the molecular weight was measured by GPC (gel permeation chromatography), the weight average molecular weight (Mw) was 500. As GPC, Tosoh Co., Ltd. product: HLS-8120GPC (column: TSK gel series) was used, The weight average molecular weight was calculated | required in the above-mentioned measurement conditions and the above-mentioned polystyrene conversion.

(Preparation of carbon black-dispersed polyamic acid oligomer solution (B-1))
In 20 g of the 20% by mass polyamic acid oligomer solution (A-1), 80 g of dried oxidized carbon black (SPECIAL BLACK4, manufactured by Orion Engineered Carbons, pH 4.0, volatile content: 14.0% by mass) And 984 g of N-methyl-2-pyrrolidone was added. This solution was treated with a ball mill for 6 hours to obtain a carbon black-dispersed polyamic acid oligomer solution (B-1).

(Formation of adhesive layer)
Carbon black-dispersed polyamic acid oligomer solution (B-1) 100 parts Epoxy resin 10 parts (Bisphenol A type epoxy resin, jER828, manufactured by Mitsubishi Chemical Corporation)
The mixture was mixed with a homogenizer for 1 hour and then applied to the substrate surface by brushing. N-methyl-2-pyrrolidone was used for viscosity adjustment. While rotating the substrate (shaft), a drying treatment was performed for 30 minutes under the condition of a temperature of 120 ° C. to form an adhesive layer having a thickness of 20 μm.
The gel fraction of the obtained adhesive layer was 95%.

-Formation of elastic layer-
A mixture having the following composition was kneaded with an open roll, an elastic layer was formed on the surface of the base material on which the adhesive layer had been formed using an extrusion molding machine, and vulcanized. At this time, the substrate (shaft) conveyance path had an outer dimension of 8 mmφ, and the substrate used had an outer diameter of 8 mmφ and a length of 350 mm. Further, as a crosshead extrusion apparatus, a 40 mm extruder manufactured by Mitsuba Seisakusho and a crosshead die having a die nozzle inner diameter of 13 mmφ were used.
Substrate clogging did not occur during extrusion molding. The friction coefficient of the adhesive layer at that time was 0.67.

・ Rubber (Epichlorohydrin ethylene oxide allyl glycidyl ether copolymer rubber, Gechron 3106: manufactured by Nippon Zeon Co., Ltd.) 100 parts ・ Conducting agent (Carbon Black Asahi Thermal: Asahi Carbon Co., Ltd.) 15 parts ・ Conducting agent (Ketjen Black EC: Ketjen Black)・ International part) 5 parts ・ Ionic conductive agent (lithium perchlorate) 1 part ・ Vulcanizing agent (sulfur 200 mesh: manufactured by Tsurumi Chemical Co., Ltd.) 1 part ・ Vulcanization accelerator (Noxeller DM: Ouchi Shinsei Chemical Industry) 2.0 parts ・ Vulcanization accelerator (Noxeller TT: manufactured by Ouchi Shinsei Chemical Co., Ltd.) 0.5 parts ・ Vulcanization accelerator auxiliary (Zinc oxide, zinc oxide 1 type: manufactured by Shodo Chemical Industry Co., Ltd.) 3 Parts ・ Stearic acid 1.5 parts

[Example 2]
In Example 1, a conductive roll was obtained in the same manner as in Example 1 except that the adhesive layer was formed in the same composition and the drying condition was 120 ° C. for 15 minutes.
The gel fraction of the adhesive layer was 52%. In addition, no substrate clogging occurred during the extrusion of the elastic layer.

Example 3
In Example 1, a conductive roll was obtained in the same manner as in Example 1 except that the adhesive layer was formed in the same composition and the drying condition was 120 ° C. for 10 minutes.
The gel fraction of the adhesive layer was 48%. In addition, no substrate clogging occurred during the extrusion of the elastic layer.

[Comparative Example 1]
A conductive roll was obtained in the same manner as in Example 1 except that the adhesive layer was formed by the following method in Example 1.
-Formation of adhesive layer 100 parts of polyolefin resin composition (Lord Far East, trade name: Chemlock XJ150)
Conductive agent 2.5 parts (carbon black, ketjen black EC: manufactured by ketjen black international)
The mixture was mixed with a ball mill for 1 hour and then applied to the surface of the substrate by brushing. Toluene or xylene was used for viscosity adjustment. While rotating the substrate (shaft), a drying treatment was performed for 30 minutes under the condition of a temperature of 120 ° C. to form an adhesive layer having a thickness of 20 μm.
The gel fraction of the obtained adhesive layer was 95%. In addition, no substrate clogging occurred during the extrusion of the elastic layer.

Example 4
A conductive roll was obtained in the same manner as in Example 1 except that the adhesive layer was formed by the following method in Example 1.
-Formation of adhesion layer 110 parts of carbon black-dispersed polyamic acid oligomer solution (B-1) The above was applied to the surface of the substrate by brush coating. N-methyl-2-pyrrolidone was used for viscosity adjustment. While rotating the substrate (shaft), a drying treatment was performed for 30 minutes under the condition of a temperature of 120 ° C. to form an adhesive layer having a thickness of 20 μm.
The gel fraction of the obtained adhesive layer was 91%.

[Evaluation]
-Measurement of gel fraction The measurement of the gel fraction of a surface layer was performed according to JIS-K6796 (1998). Cut out 1 part by mass of the adhesive layer of the conductive roll and measure the mass. This was taken as the mass of the resin before solvent extraction. After dissolving in a solvent toluene (10 parts by mass) and soaking for 24 hours, the residual resin film was removed by filtration and the mass was measured. Let this mass be the mass after extraction. From these, the gel fraction was calculated according to the following formula.
Gel fraction (%) = ((mass after extraction) / (mass of resin before solvent extraction)) × 100

-Surface condition of the substrate After storing the conductive roll in a high temperature and high humidity (45 ° C, 95% RH) environment for 10 days, the surface state was observed and the elastic layer including the surface layer was peeled off to observe the surface of the substrate. . The results are shown in Table 1.
A: Surface state before elastic layer formation and no change B: Pinholes were observed in at least one of the adhesive layer and the conductive support C: The conductive support was corroded and raised, and the adhesive layer and the conductive support There was peeling on at least one side

-Adhesiveness In order to see the adhesive strength of the adhesive layer, the elastic layer portion of the conductive roll was cut with a cutter, and the elastic layer was peeled off by hand.
A: It was difficult to peel off due to strong adhesion, or the elastic layer was broken.
B: Although there is resistance at the interface between the conductive support and the adhesive layer or the interface between the adhesive layer and the elastic layer, it can be peeled off.
C: Peel easily at the interface between the conductive support and the adhesive layer or at the interface between the adhesive layer and the elastic layer.

-Initial image quality A conductive roll is mounted as a conductive roll on the drum cartridge of a color copier DocuCenter Color a450 (manufactured by Fuji Xerox Co., Ltd.). A 50% halftone image was printed and the image quality was evaluated according to the following criteria.
A: Density unevenness, white point, and color point are not generated.
B: Density unevenness, white spots, and color spots are partially generated.
C: Density unevenness, white spots, and color spots are generated as a whole.

・ Charge maintenance property A conductive roll is mounted on a drum cartridge of DocuCentreColor400CP (manufactured by Fuji Xerox Co., Ltd.), and after 50,000 sheets of A4 printing test (50,000 sheets at 10 ° C in 15% RH environment), DocuCenterColor400CP With the following criteria, the image density unevenness when a 50% halftone image was printed was determined.
A: There is no image density unevenness at all.
B: Image density unevenness partially occurs.
C: Image density unevenness occurs throughout.

-Shape accuracy The shape after forming a conductive roll was measured using a laser outer diameter measuring instrument and evaluated according to the following criteria.
A: No irregularities on the surface due to peeling of the adhesive layer B: There are irregularities on the surface due to peeling of the adhesive layer, but they are extremely small and have no problem in image quality.
C: A level that causes many surface irregularities due to peeling of the adhesive layer and causes a problem in image quality.

DESCRIPTION OF SYMBOLS 10 Image carrier, 12 Charging device, 14 Exposure device, 16 Developing device, 18 Transfer device, 20 Cleaning device, 22 Fixing device, 24 Housing, 24A Opening, 24B Opening, 24C Mounting rail, 30 Base material, 31 Conductive elastic layer, 32 conductive outermost layer, 33 adhesive layer, 101 image forming apparatus, 102 process cartridge, 121 conductive roll, 122 cleaning member, 123 conductive bearing, 122A base material, 122B elastic layer, 124 power source, 210 Rubber roll manufacturing device, 212 discharger, 214 pressurizer, 216 drawer, 218 rubber material supply unit, 220 extrusion unit, 222 cored bar, 224 cored bar supply unit, 226 body unit, 228 screw, 230 drive motor, 232 slot 234 case, 236 mandrel, 238 discharge Head, 240 retaining member, 242 retaining member, 244 an annular passage, 246 through hole, 248 junction region, 250 rollers, 252 belt, 254 driving roller, 256 rubber roller portion

Claims (7)

A conductive substrate;
On the outer peripheral surface of the base material, at least one of a polyimide resin and a polyimide resin precursor is contained, and the total content of the polyimide resin and the polyimide resin precursor with respect to all the resins and resin precursors is 50% by mass or more. A conductive adhesive layer,
A conductive elastic layer on the adhesive layer;
A conductive roll having   The conductive roll according to claim 1, comprising a crosslinked polymer with an epoxy resin as at least one of the polyimide resin and the polyimide resin precursor.   The conductive roll according to claim 1 or 2, wherein the adhesive layer has a gel fraction of 50% or more. The electroconductive roll as described in any one of Claims 1-3 is provided,
A charging device for charging the member to be charged by bringing the conductive roll into contact with the member to be charged. An image carrier,
A charging device comprising the conductive roll according to any one of claims 1 to 3, and charging the image carrier by bringing the conductive roller into contact with the image carrier,
With
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
A charging device comprising the conductive roll according to any one of claims 1 to 3, and charging the image carrier by bringing the conductive roller into contact with the image carrier,
A latent image forming apparatus for forming a latent image on the surface of the charged image carrier;
A developing device for developing a latent image formed on the surface of the image carrier with toner to form a toner image;
A transfer device for transferring the toner image formed on the surface of the image carrier to a recording medium;
An image forming apparatus comprising: On the outer peripheral surface of the conductive base material, at least one of a polyimide resin and a polyimide resin precursor is contained, and the total content of the polyimide resin and the polyimide resin precursor with respect to all the resins and resin precursors is 50% by mass. An adhesive layer forming step of forming the conductive adhesive layer as described above;
Using an extrusion molding machine, the base material on which the adhesive layer is formed is supplied to the cross head while being inserted through a supply path having an inner diameter smaller than the outer diameter including the adhesive layer of the base material, and the cross head An elastic layer forming step of forming a conductive elastic layer by applying a material for forming an elastic layer on the adhesive layer,
The manufacturing method of the conductive roll which has this.