JP2018084650A - Belt member, fixing device, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a belt member that reduces peeling of an elastic layer from a metal layer.SOLUTION: A belt member comprises: a metal layer 10B that has concave parts 108 with a depth of 1 nm or more and 100 nm or less on its outer peripheral surface, where the atomic composition ratio of oxygen atoms in the outer peripheral surface is 40 atom% or more and 80 atom% or less; and an elastic layer 10D that is arranged on the outer peripheral side of the metal layer 10B in direct contact with the metal layer 10B or with an adhesive layer 10C therebetween.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a belt member, a fixing device, and an image forming apparatus.

  In recent years, a fixing device for an image forming apparatus that performs fixing by heating a belt member by an electromagnetic induction heating method has been proposed.

  For example, Patent Document 1 discloses that in an endless belt for electrophotography that generates heat by generating eddy current using electromagnetic induction, the endless belt is provided at least on the metal layer and on the outer peripheral side of the metal layer. An endless belt including an elastic layer having a hardness defined by JIS type A of 35 degrees or less is disclosed.

JP 2004-053713 A

In the belt member in which the elastic layer is arranged on the outer peripheral side of the metal layer, even when the adhesive layer is interposed between the metal layer and the elastic layer, the belt member is repeatedly rotated or pressurized from the outside. Depending on the use condition, peeling may occur between the metal layer and the elastic layer.
In the aspect in which the elastic layer is disposed directly on the outer peripheral side of the metal layer or through the adhesive layer, the present invention provides an outer periphery of the metal layer when the outer peripheral surface of the metal layer does not have a recess. An object of the present invention is to provide a belt member in which peeling between the metal layer and the elastic layer is suppressed as compared with the case where the atomic composition ratio of oxygen atoms on the surface is less than 40 atom%.

  In order to achieve the above object, the following invention is provided.

The invention according to claim 1 is a tubular substrate,
A metal layer having a recess having a depth of 1 nm or more and 100 nm or less on the outer peripheral surface and an atomic composition ratio of oxygen atoms on the outer peripheral surface being 40 atom% or more and 80 atom% or less;
On the outer peripheral side of the metal layer, an elastic layer disposed in direct contact with the metal layer or via an adhesive layer;
A belt member.

The invention according to claim 2
2. The belt member according to claim 1, wherein at least a layer constituting the outer peripheral surface of the metal layer is a nickel plating layer.

The invention according to claim 3
The belt member according to claim 1 or 2, wherein the elastic layer is disposed on an outer peripheral side of the metal layer via the adhesive layer, and the adhesive layer contains a silane coupling agent.

The invention according to claim 4
The belt member according to claim 1 or 2, wherein the elastic layer is disposed in direct contact with the outer peripheral side of the metal layer, and the elastic layer contains silicone rubber.

The invention according to claim 5
The belt member according to any one of claims 1 to 4, wherein the metal layer is a layer having at least an electromagnetic induction metal layer that generates heat by electromagnetic induction,
A pressure member that pressurizes the outer peripheral surface of the belt member;
An electromagnetic induction device that heats the electromagnetic induction metal layer by electromagnetic induction;
Have
A fixing device that fixes a toner image to the recording medium by sandwiching a recording medium having an unfixed toner image formed on the surface between the belt member and the pressure member.

The invention according to claim 6
An image carrier,
A charging device for charging the surface of the image carrier;
An electrostatic latent image forming apparatus that forms an electrostatic latent image on the surface of the charged image carrier;
A developing device for developing the electrostatic latent image formed on the surface of the image carrier with toner to form a toner image;
A transfer device for transferring a toner image formed on the surface of the image carrier to a recording medium;
The fixing device according to claim 5, wherein the toner image is fixed to the recording medium.
An image forming apparatus.

According to the invention according to claim 1 or 2, in an aspect in which the elastic layer is disposed on the outer peripheral side of the metal layer directly in contact with the metal layer or through the adhesive layer, the recess is formed on the outer peripheral surface of the metal layer. Is provided, a belt member in which peeling between the metal layer and the elastic layer is suppressed as compared with the case where the atomic composition ratio of oxygen atoms on the outer peripheral surface of the metal layer is less than 40 atom% is provided.
According to the invention according to claim 3, in the aspect in which the elastic layer is disposed on the outer peripheral side of the metal layer via the adhesive layer, the adhesive layer is a layer that does not contain a silane coupling agent as an adhesive. In comparison, a belt member in which peeling between the metal layer and the elastic layer is suppressed is provided.
According to the invention according to claim 4, in the aspect in which the elastic layer is disposed on the outer peripheral side of the metal layer directly in contact with the metal layer, the elastic layer is a layer that does not contain silicone rubber as an elastic material. A belt member in which peeling between the metal layer and the elastic layer is suppressed is provided.

  According to the invention which concerns on Claim 5 or 6, in the aspect using the belt member by which an elastic layer is arrange | positioned through the adhesive layer directly in contact with this metal layer on the outer peripheral side of a metal layer, this belt When the member does not have a recess on the outer peripheral surface of the metal layer, the peeling between the metal layer and the elastic layer in the belt member is suppressed as compared with the case where the atomic composition ratio of oxygen atoms on the outer peripheral surface of the metal layer is less than 40 atom%. A fixing device and an image forming apparatus are provided.

It is an expanded sectional view expanding and showing a portion of a metal layer, an adhesive layer, and an elastic layer in an example of a belt member concerning this embodiment. It is a schematic sectional drawing which shows an example of the layer structure of the belt member which concerns on this embodiment. 1 is a schematic configuration diagram illustrating an example of a fixing device according to an exemplary embodiment. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

<Belt member>
The belt member according to the present embodiment includes at least a metal layer, and an elastic layer that is in direct contact with the metal layer or disposed via an adhesive layer on the outer peripheral side of the metal layer.
The metal layer has a recess having a depth of 1 nm or more and 100 nm or less on the outer peripheral surface. In the metal layer, the atomic composition ratio of oxygen atoms (O) on the outer peripheral surface (ratio to the total raw material constituting the outer peripheral surface) is 40 atom% or more and 80 atom% or less.

In this embodiment, by having said structure, peeling with a metal layer and an elastic layer is suppressed.
The reason is guessed as follows.

Conventionally, belt members in which an elastic layer such as a rubber layer is laminated on the outer peripheral side of a metal layer have been used in various fields. As a specific example, it has a metal layer that includes at least an electromagnetic induction metal layer that generates heat by electromagnetic induction, and an elastic layer that is provided on the outer peripheral side of the metal layer in view of imparting elasticity against external pressure. Examples thereof include an electromagnetic induction heating belt, and the like, for example, used for a fixing belt for a fixing device in an image forming apparatus.
In addition, when forming elastic layers, such as a rubber layer, on a metal layer, generally providing an adhesive bond layer (primer layer) between both is performed from a viewpoint of improving adhesive force. However, even belt members with an elastic layer laminated on a metal layer through an adhesive layer (primer layer) in order to increase the adhesive force are repeatedly driven to rotate or pressurized from the outside. Depending on the situation, peeling may occur between the metal layer and the elastic layer. In particular, when the belt member is used as a fixing belt in a fixing device in an image forming apparatus, the belt member is rotationally driven and pressure is applied from a pressure member disposed in contact with the outer peripheral surface of the belt member. In some cases, stress is applied in the circumferential direction of the belt member, and this stress is concentrated between the metal layer and the elastic layer, and the elastic layer is peeled off from the metal layer.

On the other hand, in the belt member according to this embodiment, first, the atomic composition ratio of oxygen atoms (O) on the outer peripheral surface of the metal layer is in the above range. The atomic composition ratio of oxygen atoms on the outer peripheral surface being in the above range is an indicator that a functional group such as a hydroxyl group “—OH” or an oxygen atom “O” is appropriately present on the surface of the metal layer. . These functional groups such as hydroxyl group “—OH” and oxygen atom “O” are chemically bonded to the compound constituting the adhesive (primer) and the compound constituting the elastic material (rubber material, etc.) in the elastic layer. Play the role of forming
In general, the surface of the metal layer made of metal generally has few functional groups such as hydroxyl groups and oxygen atoms that can react with the compound constituting the adhesive (primer). . In addition, when the metal layer is formed and left in an oxygen atmosphere (such as in the air) with its surface exposed, the formation of an oxide film on the surface of the metal layer proceeds and passivation proceeds. The functional groups present tend to decrease further. Therefore, it is considered that a bond due to this functional group is hardly formed between the metal layer and the adhesive layer.
However, in the belt member according to the present embodiment, functional groups such as hydroxyl groups and oxygen atoms are appropriately present on the surface of the metal layer as described above, and these functional groups play a role of forming chemical bonds. Therefore, in this embodiment, if the elastic layer is disposed on the outer peripheral side of the metal layer via an adhesive layer (primer layer), the functional group on the outer peripheral surface of the metal layer and the compound constituting the adhesive layer A bond is formed between the two, and the adhesion is increased. On the other hand, if the elastic layer is arranged directly on the outer peripheral side of the metal layer without an adhesive layer, it is between the functional group on the outer peripheral surface of the metal layer and the compound constituting the elastic material in the elastic layer. It is considered that a bond is formed by this, and the adhesive force is also increased.
Secondly, the belt member according to the present embodiment has a recess having a depth of 1 nm or more and 100 nm or less on the outer peripheral surface of the metal layer, and also due to the anchoring effect (anchor effect) due to such fine unevenness. It is thought that the adhesive strength can be increased.

  Even if the belt member according to the present embodiment is repeatedly rotated or pressed from the outside due to the improvement of the adhesive force, the metal layer and the elastic layer are peeled off. Is presumed to be suppressed.

-Concave part The belt member concerning this embodiment has a recessed part in the outer peripheral surface of a metal layer.
Here, an example will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view showing an example of a belt member according to this embodiment in which an elastic layer is provided on the outer peripheral side of a metal layer via an adhesive layer. As shown in FIG. 1, the adhesive layer 10C and the elastic layer 10D are laminated on the metal layer 10B, and the recesses 108 are dotted on the outer peripheral surface of the metal layer 10B.
The preferable range of the depth, opening width, and density of the recess 108 will be described below.

The recess 108 has a depth (average depth) of 1 nm or more and 100 nm or less. When the depth of the recess 108 is 1 nm or more, the adhesive force is improved by the anchor effect, and the peeling of the elastic layer 10D from the metal layer 10B is suppressed.
The depth (average depth) of the recess 108 is preferably 2 nm or more and 100 nm or less, more preferably 5 nm or more and 100 nm or less, from the viewpoint of improving the adhesive strength.
On the other hand, the depth (average depth) of the recess 108 is preferably 1 nm or more and 50 nm or less, more preferably 1 nm or more and 20 nm or less, and further preferably 1 nm or more and 10 nm or less from the viewpoint of ease of forming the recess. It is.
Therefore, from this viewpoint, the depth (average depth) of the recess 108 is preferably 2 nm or more and 20 nm or less, and more preferably 5 nm or more and 10 nm or less.

The opening width of the concave portion 108 (average value of the length of the longest portion of the opening surface) is preferably 1 nm or more and 100 nm or less, more preferably 2 nm or more and 90 nm or less, and further preferably 5 nm or more and 80 nm or less.
When the opening width of the recess 108 is 1 nm or more, the adhesive force is improved by the anchor effect, and peeling of the elastic layer 10D from the metal layer 10B is suppressed.

The density of the recesses 108 (average number of recesses 108 per 1 μm ² ) is preferably 3 / μm ² or more and 100000 / μm ² or less, more preferably 5 / μm ² or more and 100000 / μm ² or less. More preferably, it is 10 pieces / μm ² or more and 100,000 pieces / μm ² or less.
When the density of the recesses 108 is 3 / μm ² or more, the adhesive force is improved by the anchor effect, and the peeling of the elastic layer 10D from the metal layer 10B is suppressed. On the other hand, when the number of dense paths of the concave portions 108 is 100000 pieces / μm ² or less, coalescence of the concave portions 108 is suppressed, and a shape capable of exhibiting an anchor effect is obtained, and an adhesive force is obtained.

In addition, the depth of the recessed part 108 refers to the length from the opening surface of the recessed part to the deepest part, and in the case of the recessed part 108 shown in FIG. 1, it refers to the length of the part indicated by D1 or D2.
Further, the opening width of the concave portion 108 refers to the length of the longest portion of the opening surface, and in the case of the concave portion 108 shown in FIG. 1, it refers to the length of the portion indicated by W1 or W2.
The depth and the opening width of the recess 108 are observed on the outer peripheral surface of the metal layer 10B using an atomic force microscope (AFM, manufactured by SII Nano Technology, product name: S-image + NanoNavi2). The aperture width (longest aperture surface length) and maximum depth are measured for 108, and the average value is calculated. Further, the density is calculated by counting the number of the recesses 108 and calculating the average number of existence per 1 μm ² therefrom.

-Atomic composition ratio In the belt member according to this embodiment, the atomic composition ratio of oxygen atoms (O) on the outer peripheral surface of the metal layer (the ratio to the total raw materials constituting the outer peripheral surface) is 40 atom% or more and 80 atom% or less, preferably It is 42 atom% or more and 80 atom% or less, More preferably, it is 45 atom% or more and 80 atom% or less.
It can be said that the atomic composition ratio of oxygen atoms is 40 atom% or more indicates that functional groups such as hydroxyl groups “—OH” and oxygen atoms “O” are present appropriately on the surface of the metal layer, Peeling of the elastic layer 10D from the metal layer 10B is suppressed. On the other hand, when the atomic composition ratio of oxygen atoms is 80 atom% or less, it can be said that it is not completely covered with the oxide film, and peeling of the elastic layer 10D from the metal layer 10B is suppressed.

The atomic composition ratio (oxygen (O)) on the outer peripheral surface of the metal layer is measured by X-ray photoelectric spectroscopy (XPS).
The measurement is performed under the conditions (MgKα line, 10 kV, 20A) using an X-ray photoelectron spectroscopic analyzer (manufactured by JEOL Ltd., product name: JPS-9010MX), and from the peak intensity of each element. Ask.

  In addition, when performing these measurements from a state in which an adhesive layer, an elastic layer, etc. are already formed on the metal layer, the adhesive layer, the elastic layer, etc. are peeled off (for example, cut out with a knife or dissolved with a solvent) The measurement is performed after the outer peripheral surface of the metal layer is exposed.

-Achieving method The method for forming the depth recesses in the above-mentioned range on the outer peripheral surface of the metal layer and the method for controlling the atomic composition ratio of oxygen atoms (O) on the outer peripheral surface of the metal layer to the aforementioned ranges are particularly limited. It is not something. For example, according to the surface treatment method described in the following (1) or (2), the formation of the recess and the control of the atomic composition ratio of oxygen atoms can be performed by one treatment.

(1) Method of generating bubbles in the liquid while etching the surface of the metal layer with an etching solution The surface of the metal layer is immersed in the etching solution (for example, a mixed solution of nitric acid and hydrogen peroxide solution). And a method of generating bubbles in the etching solution and bursting the bubbles. By etching the metal layer, the oxide film formed on the surface is removed, and a new surface of the metal layer is exposed. By the presence of functional groups (hydroxyl group (—OH), oxygen (O), etc.) on the exposed surface It is considered that the atomic composition ratio of oxygen atoms is controlled within the aforementioned range. In addition, it is considered that when the bubbles are generated in the etching solution at this time, the bubbles burst on the surface of the metal layer to form a recess.
The depth and opening width of the recesses are adjusted by controlling the size of the bubbles to be generated, and the density of the recesses is adjusted by controlling the density of the bubbles to be generated.

The method for generating bubbles in the etching solution is not particularly limited, and examples thereof include the following methods.
-Method by ultrasonic vibration: A method in which bubbles are generated by applying ultrasonic vibration to an etching solution in which a metal layer is immersed may be mentioned. According to the ultrasonic vibration, the size and density of bubbles generated by adjusting the output and frequency can be easily controlled. The application time of ultrasonic vibration is preferably, for example, 1 second to 30 seconds, and more preferably 2 seconds to 25 seconds.
-Method of dissolving gas in the liquid by pressure: A method of generating bubbles by applying pressure to the etching solution in which the metal layer is immersed to dissolve the gas (for example, the atmosphere) in the liquid and then releasing the pressure. Can be mentioned. It is possible to control the size and density of bubbles generated by adjusting the pressure applied and the speed at which the pressure is released.

Examples of the etching solution that can be used include hydrochloric acid, sulfuric acid, and the like in addition to the mixed solution of nitric acid and hydrogen peroxide solution.
Among these, a mixed solution of nitric acid and hydrogen peroxide solution is excellent in handleability.

(2) Method of generating bubbles in the liquid while oxidizing the surface of the metal layer in the ozone-containing liquid While oxidizing the metal layer surface by immersing the outer peripheral surface of the metal layer in an ozone-containing liquid (for example, ozone-dissolved water) And a method of generating bubbles in the ozone-containing liquid and rupturing the bubbles. By immersing the metal layer in an ozone-containing liquid, the surface is oxidized to generate functional groups (hydroxyl group (—OH), oxygen (O), etc.), and the atomic composition ratio of oxygen atoms is controlled within the aforementioned range. it is conceivable that. Moreover, it is thought that a recessed part is formed when this bubble bursts on the surface of a metal layer by generating a bubble in an ozone containing liquid in that case.
The depth and opening width of the recesses are adjusted by controlling the size of the bubbles to be generated, and the density of the recesses is adjusted by controlling the density of the bubbles to be generated.
The method for generating bubbles in the ozone-containing liquid is not particularly limited, and examples thereof include the above-described ultrasonic vibration method and the method of dissolving gas in the liquid with pressure.

  Next, each layer constituting the belt member according to the present embodiment will be described in detail.

Here, the configuration of the belt member according to the present embodiment will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram illustrating an example of a belt member according to the present embodiment, and is a configuration diagram illustrating a belt member used as a fixing belt in the image forming apparatus.
The belt member 10 shown in FIG. 1 has a layer configuration in which a metal layer 10B, an adhesive layer 10C, an elastic layer 10D, and a release layer 10E are sequentially laminated on the outer peripheral surface of a tubular base material 10A. It is an endless belt. The metal layer 10B is a multilayer metal layer in which a plurality of layers are stacked, and the base metal layer 102, the electromagnetic induction metal layer 104 that self-heats by electromagnetic induction, and the metal protective layer 106 are stacked in this order. Being done.
And the metal protective layer 106 which comprises the outer peripheral surface of the metal layer 10B has the recessed part whose depth is the said range, and the atomic composition ratio of an oxygen atom is the above-mentioned range.

In the following, the belt member 10 having the configuration shown in FIG. 1 will be described as an example, but the present embodiment is not limited to this structure. For example, FIG. 1 shows a structure in which a base metal layer 102, an electromagnetic induction metal layer 104, and a metal protective layer 106 are stacked in this order as the metal layer 10B, but the number of stacked metal layers is different. Also good. For example, it may consist of a single metal layer. Further, the adhesive layer 10C may not be provided, and the release layer 10E may not be provided.
In the following description, the reference numerals of each layer may be omitted.

[Substrate 10A]
For example, in the case where the adjacent metal layer 10B has a layer that self-heats due to electromagnetic induction action, the base material 10A is preferably a layer that can maintain high strength with little change in physical properties even in a heated state. For this reason, it is preferable that the base material 10A is mainly composed of a heat-resistant resin (in the present specification, “mainly” and “main component” mean that the mass ratio is 50% or more, and Is also synonymous).

  In the case of the base material 10A mainly composed of a heat-resistant resin, slidability with the pressing member in contact with the inner peripheral surface of the belt member is ensured, and the life of the pressing member is extended. Furthermore, since the heat resistant resin has a heat insulating effect, the heat from the metal layer 10 </ b> B can be efficiently transferred to the outer peripheral surface side without escaping to the pressing member.

Examples of the heat-resistant resin that can form the base material 10A include liquid crystal materials such as polyimide, aromatic polyamide, and thermotropic liquid crystal polymer, and high heat-resistant and high-strength resins. Besides these, polyester, polyethylene terephthalate Polyether sulfone, polyether ketone, polysulfone, polyimide amide, etc. are used. Among these, polyimide is desirable.
Moreover, you may improve the heat insulation effect further by adding the filler with a heat insulation effect in a heat resistant resin, or making a heat resistant resin foam.

  The thickness of the base material 10A is preferably in the range of 10 μm or more and 200 μm or less, more preferably in the range of 30 μm or more and 100 μm or less, from the viewpoint of achieving both rigidity and flexibility for realizing long-term repeated circumferential conveyance of the belt member. .

Further, the tensile strength of the base material 10A preferably satisfies 200 MPa or more (more preferably 250 MPa or more). The tensile strength of a base material can be adjusted with the kind of resin, the kind of filler, and addition amount.
In addition, the tensile strength (MPa) of the base material is obtained by cutting the base material into a strip shape having a width of 5 mm and installing the base material in a tensile tester Model 1605N (manufactured by Aiko Engineering Co., Ltd.) and pulling at a constant speed of 10 mm / sec. Measured with tensile strength at break (MPa).

[Underlying metal layer 102]
The base metal layer 102 is a layer formed in advance in order to form the electromagnetic induction metal layer 104 on the outer peripheral surface of the base material 10A by an electrolytic plating method. The formation of the electromagnetic induction metal layer 104 is preferably performed by an electrolytic plating method from the viewpoint of cost or the like. However, when the base material 10A mainly composed of a resin is used, it is not easy to perform the direct electrolytic plating. From the viewpoint of forming the induction metal layer 104, the base metal layer 102 is preferably provided.

  Examples of the method for forming the base metal layer 102 on the outer peripheral surface of the substrate 10A include an electroless plating method, a sputtering method, a vapor deposition method, and the like, and a chemical plating method (electroless plating method) from the viewpoint of easiness of film formation. Of these, general electroless nickel plating layers, electroless copper plating layers, and the like are preferable.

  In addition, before forming the base metal layer 102 on the outer peripheral surface of the base material 10A by the electroless plating method, the surface roughness of the outer peripheral surface of the base material 10A is preliminarily roughened so that the metal particles easily adhere (roughness). Surface treatment) may be performed. Examples of the roughening treatment include a method of roughening the surface of the substrate 10A by sandblasting using alumina abrasive grains or the like, cutting, sandpaper polishing, or the like.

  The thickness of the base metal layer 102 is desirably in the range of 0.1 μm to 5 μm, and more desirably in the range of 0.3 μm to 3 μm.

  The thickness of each layer constituting the belt member according to the present embodiment is determined by accelerating a scanning electron microscope (“JSM6700F” manufactured by JEOL Ltd.) by preparing a cross section in the circumferential direction and the axial direction of the cylindrical body of the belt member. It is the value which measured the film thickness from the observation image in voltage 2.0kV and 5000 times.

[Electromagnetic induction metal layer 104]
The electromagnetic induction metal layer 104 is a heat generation layer having a function of generating heat by an eddy current generated in the layer when a magnetic field is applied, and is made of a metal that generates an electromagnetic induction effect.
As a metal that generates electromagnetic induction, for example, a single metal such as nickel, iron, copper, gold, silver, aluminum, chromium, tin, zinc, or an alloy containing two or more kinds of metals may be selected. . In consideration of cost, heat generation performance, and workability, copper, nickel, aluminum, iron, and chromium are suitable, and among these, copper or an alloy containing copper as a main component is particularly desirable.

  The electromagnetic induction metal layer 104 is formed by performing a known method, for example, electrolytic plating.

  The optimum thickness of the electromagnetic induction metal layer 104 differs depending on the metal material. For example, when copper is used for the electromagnetic induction metal layer 104, the thickness of the electromagnetic induction metal layer 104 is efficiently generated from the viewpoint of heat generation. Is preferably in the range of 3 μm to 50 μm, more preferably in the range of 3 μm to 30 μm, and still more preferably in the range of 5 μm to 20 μm.

[Metal protective layer 106]
A metal protective layer is provided on the outer peripheral surface side of the electromagnetic induction metal layer 104 in order to improve the film strength, suppress cracks due to repeated deformation, oxidative deterioration due to repeated heating for a long time, and maintain heat generation characteristics. It is preferably provided in contact with the electromagnetic induction metal layer 104.
And the belt member which concerns on this embodiment has the recessed part whose depth is the said range on the outer peripheral surface of the metal layer 10B, and the atomic composition ratio of an oxygen atom is the above-mentioned range.

The metal protective layer 106 is a thin film with high breaking strength, high durability and high oxidation resistance, and is preferably an oxidation resistant metal. Specifically, for example, it may be configured to contain copper or nickel, and is particularly an oxidation-resistant metal from the viewpoint of suppressing the occurrence of cracks due to repeated deformation and oxidative deterioration due to repeated heating. It is desirable to include nickel (or a nickel alloy).
Moreover, it is desirable that the outer peripheral surface of the metal layer 10B contains nickel (or nickel alloy) from the viewpoint of easily controlling the atomic composition ratio of oxygen atoms within the aforementioned range.

  The optimum thickness of the metal protective layer 106 differs depending on the material. For example, when the metal protective layer 106 is formed of nickel, flexibility is obtained while suppressing cracking due to insufficient breaking strength. From the viewpoint of suppressing the warm-up time without increasing the heat capacity of the film itself, the range is preferably 2 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less, and more preferably 5 μm or more and 10 μm or less. More preferably, it is in the range.

  As a method of forming the metal protective layer 106, in consideration of workability with a thin film, it is preferable to form the metal protective layer 106 by electrolytic plating, and among these, electrolytic nickel plating having high strength is more preferable.

  When forming by an electroplating method, a plating solution containing metal ions such as nickel ions is prepared, and the substrate 10A having the base metal layer 102 and the electromagnetic induction metal layer 104 is immersed in this plating solution to perform electrolytic plating. An electrolytic plating layer (metal protective layer 106) having a required thickness is formed.

[Adhesive layer 10C]
An adhesive layer 10C may be interposed between the layer constituting the outer peripheral surface of the metal layer 10B (the metal protective layer 106 in FIG. 1) and the elastic layer 10D from the viewpoint of improving the adhesion between the two layers. .

  From the viewpoint of thermal conductivity, the adhesive layer 10C is usually provided as a thin film layer (for example, 1 μm or less). The thickness of the adhesive layer 10C is preferably 0.1 μm or more and 1 μm or less, and more preferably 0.2 μm or more and 0.5 μm or less from the viewpoint of ease of forming the adhesive layer.

  As the adhesive used for the adhesive layer 10C, an adhesive having little change in physical properties even when the adjacent metal layer 10B generates heat and having excellent heat transfer to the outer peripheral surface side is preferable. Specific examples include silane coupling agent-based adhesives, silicone-based adhesives, epoxy resin-based adhesives, and urethane resin-based adhesives.

Among these, a silane coupling agent adhesive is more preferable. Since the adhesive layer 10C contains a silane coupling agent adhesive, the adhesive is formed by forming a bond with a functional group (hydroxyl group (—OH), oxygen atom (O), etc.) on the outer peripheral surface of the metal layer 10B. Adhesion with the layer 10C becomes stronger and the occurrence of peeling is more easily suppressed.
Examples of silane coupling agent adhesives include vinyl group silane coupling agents, epoxy group silane coupling agents, amino group silane coupling agents, methacryl group silane coupling agents, and styryl group silane coupling agents. And amino group-based silane coupling agents, among which vinyl group coupling agents are more preferable.

[Elastic layer 10D]
The elastic layer 10D is a layer provided from the viewpoint of imparting elasticity to the pressure applied from the outer peripheral side to the belt member. For example, when used as a fixing belt in an image forming apparatus, the toner on the recording medium This is a layer that follows the unevenness of the image and plays a role of bringing the surface of the belt member into close contact with the toner image. In particular, when a multicolor image is formed, the elastic layer 10D makes it easy to obtain an image in which the color development deterioration and the gloss unevenness due to the heating unevenness of the recording medium and the toner image are suppressed. In addition, since the elastic layer 10D is deformed in the contact area with the pressure member and a contact width can be obtained even with a low load, heat is transferred to the toner image even if the process speed (recording medium conveyance speed) is increased. The image is fixed and fixed, and even when a black and white image is formed, it is easy to increase the speed.

The elastic layer 10D is preferably made of an elastic material that can be restored to its original shape even when deformed by applying an external force of 100 Pa, for example.
Silicone rubber is preferable as the elastic material used for the elastic layer 10D. In the embodiment in which the elastic layer 10D is formed so as to be in direct contact with the outer peripheral surface of the metal layer 10B, the elastic layer 10D contains silicone rubber, so that the functional group (hydroxyl group (—OH), oxygen Formation of a bond with an atom (O) or the like makes the adhesion to the elastic layer 10D stronger and makes it easier to suppress the occurrence of peeling.

Examples of the silicone rubber include RTV silicone rubber, HTV silicone rubber, and liquid silicone rubber. Specifically, polydimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl silicone rubber (PMQ). ), Fluorosilicone rubber (FVMQ) and the like.
Examples of the commercially available product include liquid silicone rubber SE6744 manufactured by Toray Dow Corning Silicone.

  In the present embodiment, in the elastic material included in the elastic layer 10D, it is preferable that silicone rubber is a main component (that is, 50% or more in terms of mass ratio), and the content is 90% by mass or more. Is more preferable, and it is further more preferable that it is 99 mass% or less.

Other materials may be used as the elastic material for the elastic layer 10D. For example, heat-resistant rubber such as fluorine rubber can be used. Examples of the fluororubber include vinylidene fluoride rubber, tetrafluoroethylene / propylene rubber, tetrafluoroethylene / perfluoromethyl vinyl ether rubber, phosphazene rubber, and fluoropolyether.
Examples of commercially available products include Viton B-202 manufactured by DuPont Dow elastmers.

Various additives may be blended in the elastic layer 10D.
In particular, it is preferable to add a filler from the viewpoint of improving the thermal conductivity of the elastic layer 10D. The thermal conductivity of the filler is preferably 0.3 W / mK or more, more preferably 50 W / mK or more, and even more preferably 100 W / mK or more from the viewpoint of obtaining higher thermal conductivity in the elastic layer 10D.

Filler materials include carbides (for example, carbon black, carbon fiber, carbon nanotubes, etc.), titanium oxide, silicon carbide, talc, mica, kaolin, iron oxide, calcium carbonate, calcium silicate, magnesium oxide, graphite, silicon nitride And well-known inorganic fillers such as boron nitride, iron oxide, cerium oxide, aluminum oxide, magnesium carbonate, and metal silicon.
Among these, silicon nitride, silicon carbide, graphite, boron nitride, and carbide are preferable from the viewpoint of thermal conductivity.

  The filler content of the elastic layer 10D may be determined by the required thermal conductivity, mechanical strength, and the like. For example, the content of the filler in the elastic layer 10D is preferably in the range of 1% by mass to 20% by mass, more preferably in the range of 3% by mass to 15% by mass, and more preferably in the range of 5% by mass to 10% by mass. A range is further preferred.

  Examples of additives include softeners (paraffins, etc.), processing aids (stearic acid, etc.), anti-aging agents (amines, etc.), and vulcanizing agents (sulfur, metal oxides, peroxides, etc.). And functional fillers (such as alumina).

  The thickness of the elastic layer 10D is, for example, preferably 30 μm or more and 600 μm or less, and preferably 100 μm or more and 500 μm or less.

[Release layer 10E]
The release layer 10E is a layer for imparting releasability to the outer peripheral surface. For example, in an aspect used as a fixing belt in an image forming apparatus, fixing is performed on a surface (outer peripheral surface) on the side in contact with the recording medium. It is a layer that plays a role of suppressing the fixation of a molten toner image sometimes. Note that the release layer 10E may not be provided.

  The release layer 10E preferably includes a low surface energy material such as a fluorine-based compound as a main component. Examples of the fluorine compound include fluororubber, polytetrafluoroethylene (hereinafter referred to as “PTFE”), perfluoroalkyl vinyl ether copolymer (hereinafter referred to as “PFA”), ethylene tetrafluoride ethylene hexafluoride propylene copolymer. A fluororesin such as a polymer (hereinafter referred to as “FEP”) is exemplified, but it is not particularly limited.

  The thickness of the release layer 10E is preferably in the range of 10 μm to 100 μm, and more preferably in the range of 20 μm to 50 μm. When the thickness of the release layer 10E is 10 μm or more, wear of the release layer 10E due to repeated friction at the edge of the paper is suppressed. Further, when the thickness of the release layer 10E is 100 μm or less, the surface flexibility is maintained, the granularity of the fixed image is maintained, and the warm-up time is shortened.

A known method may be applied to form the elastic layer 10D and the release layer 10E. For example, the elastic layer 10D and the release layer 10E may be sequentially formed on the metal layer 10B by a coating method.
When the elastic layer 10D and the release layer 10E are formed on the metal layer 10B by a coating method, an appropriate layer is appropriately applied to the surface of the metal layer 10B or the surface of the elastic layer 10D before applying these layers. It is desirable to perform a pretreatment with an adhesive (primer).

  Further, when the elastic layer 10D and the release layer 10E are laminated on the metal layer 10B by a coating method, the elastic layer 10D and the release layer 10E are formed through a process of heat-treating the coated film formed. Is done. The heat treatment of the coating film may be performed in an inert gas (nitrogen gas, argon gas, etc.) atmosphere.

  Further, the release layer 10E is prepared in advance by forming a tube-like release layer, for example, by forming an adhesive layer on the inner surface of the tube and then covering the outer periphery of the elastic layer 10D. May be.

-Use-
The belt member according to the present embodiment is suitably used, for example, in an image forming apparatus. Specifically, it is used as a fixing belt, a pressure belt, or the like used in an electromagnetic induction heating type fixing device that fixes the toner image onto a recording medium on which an unfixed toner image is formed.

<Fixing device>
The fixing device according to this embodiment is configured to press the belt member according to the above-described embodiment and the outer peripheral surface of the belt member, and sandwich the recording medium on which the unfixed toner image is formed with the belt member. A pressure member, and an electromagnetic induction device that generates heat by electromagnetic induction of the metal layer of the belt member.

FIG. 3 is a schematic configuration diagram illustrating an example of a fixing device according to the present embodiment.
The fixing device 100 according to the present embodiment is an electromagnetic induction type fixing device including the belt member 10 according to the present embodiment. As shown in FIG. 3, a pressure roll (pressure member) 11 is arranged so as to press a part of the belt member 10, and contact is made between the belt member 10 and the pressure roll 11 from the viewpoint of efficient fixing. A region (nip) is formed, and the belt member 10 is curved along the circumferential surface of the pressure roll 11. In addition, from the viewpoint of ensuring the peelability of the recording medium, a bent portion is formed where the belt member bends at the end of the contact area (nip).

  The pressure roll 11 is configured such that an elastic layer 11B made of silicone rubber or the like is formed on a substrate 11A, and a release layer 11C made of a fluorine-based compound is formed on the elastic layer 11B.

  A counter member 13 is disposed inside the belt member 10 at a position facing the pressure roll 11. The facing member 13 is made of metal, heat-resistant resin, heat-resistant rubber, or the like, and has a pad 13B that is in contact with the inner peripheral surface of the belt member 10 and locally increases the pressure, and a support 13A that supports the pad 13B.

An electromagnetic induction device 12 incorporating an electromagnetic induction coil (excitation coil) 12a is provided at a position facing the pressure roll 11 (an example of a pressure member) with the belt member 10 as the center. The electromagnetic induction device 12 applies an alternating current to the electromagnetic induction coil to change the generated magnetic field by an excitation circuit, and the metal layer 10B of the belt member 10 (especially the electromagnetic induction metal layer in the belt member of the embodiment shown in FIG. 1). 104), an eddy current is generated. This eddy current is converted into heat (Joule heat) by the electric resistance of the metal layer 10B, and as a result, the surface of the belt member 10 generates heat.
The position of the electromagnetic induction device 12 is not limited to the position shown in FIG. 3. For example, the electromagnetic induction device 12 may be installed upstream of the contact region of the belt member 10 in the rotational direction B, or inside the belt member 10. It may be installed in.

In the fixing device 100 according to the present embodiment, when the driving force is transmitted to the gear fixed to the end of the belt member 10 by the driving device, the belt member 10 self-rotates in the arrow B direction, and the belt member 10 Along with the rotation, the pressure roll 11 rotates in the reverse direction, that is, in the direction of arrow C.
The recording medium 15 on which the unfixed toner image 14 is formed is passed through the contact area (nip) between the belt member 10 and the pressure roll 11 in the fixing device 100 in the direction of arrow A, and the unfixed toner image 14 is in a molten state. Is applied to the recording medium 15 by applying pressure.

<Image forming apparatus>
An image forming apparatus according to the present embodiment includes an image carrier, a charging device that charges the surface of the image carrier, and an electrostatic latent image forming device that forms an electrostatic latent image on the charged surface of the image carrier. A developing device that develops the electrostatic latent image formed on the surface of the image carrier with toner to form a toner image, and a transfer that transfers the toner image formed on the surface of the image carrier to a recording medium And a fixing device according to this embodiment for fixing the toner image to the recording medium.

FIG. 4 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present embodiment.
As shown in FIG. 4, the image forming apparatus 200 according to the present embodiment includes a photosensitive member (an example of an image holding member) 202, a charging device 204, a laser exposure device (an example of a latent image forming device) 206, a mirror 208, and development. Device 210, intermediate transfer body 212, transfer roll (an example of a transfer device) 214, cleaning device 216, static eliminator 218, fixing device 100, and paper feed device (paper feed unit 220, paper feed roller 222, registration roller 224, And a recording medium guide 226).

  When image formation is performed with the image forming apparatus 200, first, a non-contact type charging device 204 provided in the vicinity of the photoconductor 202 charges the surface of the photoconductor 202.

  Laser light corresponding to the image information (signal) of each color is irradiated from the laser exposure device 206 through the mirror 208 on the surface of the photosensitive member 202 charged by the charging device 204, thereby forming an electrostatic latent image.

  The developing device 210 forms a toner image by applying toner to the latent image formed on the surface of the photoreceptor 202. The developing device 210 includes developing devices (not shown) for the respective colors, each containing toners of four colors, cyan, magenta, yellow, and black. Each color toner is applied to the latent image formed on the surface to form a toner image.

  The toner images of the respective colors formed on the surface of the photoconductor 202 are changed in color at the contact portion between the photoconductor 202 and the intermediate transfer body 212 by a bias voltage applied between the photoconductor 202 and the intermediate transfer body 212. Each toner image is transferred onto the outer peripheral surface of the intermediate transfer body 212 so as to coincide with the image information.

The intermediate transfer member 212 has an outer peripheral surface that contacts the surface of the photoreceptor 202 and rotates in the direction of arrow E.
In addition to the photoconductor 202, a transfer roll 214 is provided around the intermediate transfer body 212.

  The intermediate transfer body 212 onto which the multicolor toner image has been transferred rotates in the direction of arrow E. The toner image on the intermediate transfer body 212 is transferred to the surface of the recording medium 15 conveyed to the contact portion in the direction of arrow A by the paper feeding device at the contact portion between the transfer roll 214 and the intermediate transfer body 212.

  The recording medium housed in the paper feeding unit 220 is fed by a recording medium push-up unit (not shown) built in the paper feeding unit 220 to feed the contact portion between the intermediate transfer body 212 and the transfer roll 214. When the recording medium 15 is pushed up to a position where it contacts the roller 222 and contacts the paper feed roller 222, the paper feed roller 222 and the registration roller 224 rotate to convey along the recording medium guide 226 in the direction of arrow A. Is done.

  The toner image transferred to the surface of the recording medium 15 moves in the direction of arrow A, and the toner image 14 is melted on the surface of the recording medium 15 in the contact area (nip) between the belt member 10 and the pressure roll 11. It is pressed and fixed on the surface of the recording medium 15. Thereby, an image fixed on the surface of the recording medium is formed.

The surface of the photoconductor 202 after the toner image is transferred to the surface of the intermediate transfer body 212 is cleaned by the cleaning device 216.
The surface of the photoconductor 202 is cleaned by the cleaning device 216 and then discharged by the charge removing device 218.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the following, “%” is based on mass unless otherwise specified.

[Example 1]
-Preparation of substrate (PI substrate) N-methyl-2-pyrrolidone (NMP) solution of polyimide precursor (polyimide varnish "U-imide AH", manufactured by Unitika Ltd.) is flow-coated onto a mold with a diameter of 30 mm. Then, the temperature was stepped up to 380 ° C. (25 ° C. → 120 ° C. for 1 hour → 250 ° C. for 1 hour → 380 ° C. for 1 hour → 25 ° C.).
Thereby, a seamless resin tubular body made of polyimide (resin single layer) having an inner diameter of 30 mm, a film thickness of 60 μm, and a width of 400 mm was obtained.

The surface of the obtained tubular seamless resin tubular body was subjected to a surface roughening treatment using a liquid honing apparatus (manufactured by Fuji Seiki, LH-8TTHiS) so that the surface roughness Ra = 0.5 μm or more and 1.0 μm or less. . The honing conditions were as follows: abrasive grain # 320, spray pressure 0.3 MPa, spray distance 100 mm, and processing time 1.5 minutes.
After the abrasive grains on the surface of the roughened seamless resin tubular body were washed away with ion-exchanged water, moisture was removed with compressed air to obtain a PI base material.

-Formation of base metal layer Next, the PI base material was incorporated in a plating jig, and an electroless copper plating layer (base metal layer) having a thickness of 0.5 µm was formed by electroless plating.

-Formation of an electromagnetic induction metal layer After forming an electroless copper plating layer (underlying metal layer), electrodes are set on both ends of the plating jig and subjected to electrolytic plating with a copper sulfate plating solution. A layer (electromagnetic induction metal layer) was formed.

-Formation of a metal protective layer Next, it immersed in the plating solution containing a nickel ion, nickel electroplating was performed, and the 9-micrometer-thick electrolytic nickel layer (metal protective layer) was formed.

-Metal layer surface treatment After forming the electrolytic nickel layer (metal protective layer), the surface of the metal protective layer was immersed in a 50:50 mixture of 10% nitric acid and 5% hydrogen peroxide, Using a sonic device (product name: US-30JS, manufactured by SND Co., Ltd.), ultrasonic vibration having an output of 200 W and a frequency of 100 kHz was applied for 5 seconds to perform surface treatment of the metal layer.
The surface of the metal protective layer was observed with an atomic force microscope (AFM), and the depth (average depth), opening width, and density of the recesses were measured by the above-described methods. Moreover, the atomic composition ratio of oxygen (O) on the surface of the metal layer protective layer was measured by X-ray photoelectric spectroscopy (XPS). The results are shown in Table 1.

-Application of adhesive On the outer peripheral surface of the formed metal protective layer, a silane coupling agent (manufactured by Dow Corning Toray, product name: DY39-111A / B) as an adhesive is 0.3 μm in thickness. This was applied to form an adhesive layer.

-Formation of elastic layer and release layer Next, liquid silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., liquid silicone rubber X34-1053) was applied to the outer peripheral surface of the metal protective layer using a spiral coater (thickness 200 μm) Then, after primary vulcanization (120 ° C., 15 minutes), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) tube (thickness 30 μm, having an adhesive layer on the inner surface) was coated and fired ( 200 ° C., 2 hours).
Thus, after an elastic layer and a release layer were sequentially formed on the outer peripheral surface, both end portions 15 mm were cut off to obtain a belt member.

[Example 2]
In Example 1, a belt member was obtained in the same manner as in Example 1 except that the metal layer surface treatment was changed to the treatment by the following method.
-Metal layer surface treatment The surface of the metal protective layer is immersed in ozone water (ozone concentration 30 ppm) generated by an ozone water generator (ED-OW-7) manufactured by Ecodesign Co., Ltd. The surface of the metal layer was subjected to surface treatment by applying ultrasonic vibration having an output of 200 W and a frequency of 100 kHz for 10 seconds using a product of USNDI, product name: US-30JS.
Table 1 shows the measurement results of the depth (average depth) of the recesses, the opening width, the density, and the atomic composition ratio of oxygen (O).

[Comparative Example 1]
In Example 1, a belt member was obtained in the same manner as in Example 1 except that the metal layer surface treatment was not performed.
As a result of observing the surface of the metal protective layer with an atomic force microscope (AFM), no recess was present. Table 1 shows the measurement results of the atomic composition ratio of oxygen (O).

<Evaluation Test 1 / Pressure Repeated Stress Test>
A belt member is installed on a friction player (Reska Co., Ltd., product name: Friction Player FPR-2000) with the elastic layer facing upward, and a load of 1 kgf is applied with a stainless steel pin from above to a 45 ° arc. I exercised. In that case, the frequency | count until peeling generate | occur | produces between the layer (metal protective layer) which comprises the outermost surface in a metal layer, and an elastic layer was measured.
The results were evaluated against the following criteria.
A (○): No occurrence up to 3000 times B (△): No occurrence up to 2000 times Occurrence up to 3000 times C (x): Occurrence up to 2000 times

<Evaluation Test 2 / Durability Test in Image Forming Apparatus>
The belt member is mounted as a fixing belt on an electromagnetic induction type fixing device in an image forming apparatus (manufactured by Fuji Xerox, model number: ApeosPort-V C7776), and 500 kpv (500 × 10 ^{3) on} copy paper C2 paper manufactured by Fuji Xerox. Image). Then, the presence or absence of generation | occurrence | production of peeling between the metal protective layer and elastic layer in a belt member was confirmed.
The results were evaluated against the following criteria.
A (○): No peeling occurred B (×): The peeling occurred

  As shown in Tables 1 and 2, compared to the comparative example that does not have a recess and the value of the atomic composition ratio of oxygen atoms does not satisfy the aforementioned range, the adhesiveness is improved and peeling is suppressed in the examples. I understand.

DESCRIPTION OF SYMBOLS 10 Belt member 10A Base material 10B Metal layer 10C Adhesive layer 10D Elastic layer 10E Release layer 11 Pressure roll 11A Base material 11B Elastic layer 11C Release layer 12 Electromagnetic induction apparatus 13 Opposing member 13A Support body 13B Pad 14 Toner image 15 Recording medium 100 Fixing device 102 Underlying metal layer 104 Electromagnetic induction metal layer 106 Metal protective layer 200 Image forming device 202 Photoconductor 204 Charging device 206 Exposure device 210 Developing device 212 Intermediate transfer member 214 Transfer roll

Claims (6)

A metal layer having a recess having a depth of 1 nm or more and 100 nm or less on the outer peripheral surface and an atomic composition ratio of oxygen atoms on the outer peripheral surface being 40 atom% or more and 80 atom% or less;
On the outer peripheral side of the metal layer, an elastic layer disposed in direct contact with the metal layer or via an adhesive layer;
A belt member.   2. The belt member according to claim 1, wherein at least a layer constituting the outer peripheral surface of the metal layer is a nickel plating layer.   The belt member according to claim 1 or 2, wherein the elastic layer is disposed on an outer peripheral side of the metal layer via the adhesive layer, and the adhesive layer contains a silane coupling agent.   The belt member according to claim 1 or 2, wherein the elastic layer is disposed in direct contact with the outer peripheral side of the metal layer, and the elastic layer contains silicone rubber. The belt member according to any one of claims 1 to 4, wherein the metal layer is a layer having at least an electromagnetic induction metal layer that generates heat by electromagnetic induction,
A pressure member that pressurizes the outer peripheral surface of the belt member;
An electromagnetic induction device that heats the electromagnetic induction metal layer by electromagnetic induction;
Have
A fixing device that fixes a toner image to the recording medium by sandwiching a recording medium having an unfixed toner image formed on the surface between the belt member and the pressure member. An image carrier,
A charging device for charging the surface of the image carrier;
An electrostatic latent image forming apparatus that forms an electrostatic latent image on the surface of the charged image carrier;
A developing device for developing the electrostatic latent image formed on the surface of the image carrier with toner to form a toner image;
A transfer device for transferring a toner image formed on the surface of the image carrier to a recording medium;
The fixing device according to claim 5, wherein the toner image is fixed to the recording medium.
An image forming apparatus.