JP2021157071A - Fixing belt - Google Patents

Abstract

To provide a fixing belt for electrophotographic apparatuses, which can suppress in separation between a metal layer and a rubber elastic body layer during endurance.SOLUTION: A primer layer 16 is composed of a cured product of a primer composition that contains an adhesive component having an amino group and an adhesive component having an alkenyl group. A rubber elastic body layer 18 is composed of a cured product of a silicone rubber composition that contains an organopolysiloxane having an alkenyl group and a crosslinking agent having a hydrosilyl group, and at least one adhesive component of an adhesive component having an epoxy group, an adhesive component having an alkenyl group, and an adhesive component having an acryloyl group. In the silicone rubber composition, the amount of hydrosilyl groups contained in the crosslinking agent is 0.3 or more and 1.0 or less in terms of molar ratio if the amount of alkenyl groups contained in the organopolysiloxane is taken as 1.0.SELECTED DRAWING: Figure 2

Description

The present invention relates to a fixing belt for an electrophotographic device, which is preferably used in a fixing process for an electrophotographic device.

In electrophotographic equipment such as copiers, printers, and facsimiles that employ the electrophotographic method, a toner image is formed on a recording medium (paper, etc.), and the image is formed by heating and pressurizing this with a fixing belt to fix it. ing. In the fixing system in electrophotographic, a method of heating the fixing belt by an electromagnetic induction heating method to perform fixing has been proposed. As a fixing belt of this type, for example, the one described in Patent Document 1 is known. Patent Document 1 describes a fixing belt having a metal layer that generates heat by electromagnetic induction on a tubular base layer, and an elastic layer containing silicone rubber on the outer peripheral side of the metal layer via an adhesive layer. ..

JP-A-2017-62403

Since stress is applied to the fixing belt in the circumferential direction during driving, peeling is likely to occur between the metal layer and the elastic layer. When the metal constituting the metal layer is a metal such as copper that is easily oxidized, the above-mentioned peeling is particularly likely to occur, and at the time of durability, peeling is likely to occur between the metal layer and the elastic layer due to the influence of heat.

An object to be solved by the present invention is to provide a fixing belt for an electrophotographic apparatus in which peeling between a metal layer and a rubber elastic body layer is suppressed during durability.

In order to solve the above problems, the fixing belt according to the present invention includes a tubular metal layer, a primer layer formed on the outer peripheral surface of the metal layer, and a rubber elastic body formed on the outer peripheral surface of the primer layer. A fixing belt for an electrophotographic apparatus having a layer, wherein the metal layer is made of copper, copper alloy, nickel, nickel alloy, silver, silver alloy, zinc, zinc alloy, tin, tin alloy, gold, gold alloy. The primer layer is composed of a cured product of a primer composition containing an adhesive component having an amino group and an adhesive component having an alkenyl group, and the rubber elastic body layer is composed of at least one of the metals. , Organopolysiloxane having an alkenyl group and a cross-linking agent having a hydrosilyl group, and at least one of an adhesive component having an epoxy group, an adhesive component having an alkenyl group, and an adhesive component having an acryloyl group. It is composed of a cured product of a silicone rubber composition, and the amount of hydrosilyl groups contained in the cross-linking agent in the silicone rubber composition is 1.0 in terms of the amount of alkenyl groups contained in the organopolysiloxane, in terms of molar ratio. , 0.3 or more and 1.0 or less.

The amount of the alkenyl group in the primer composition is preferably 0.8 or more and 3.0 or less in terms of molar ratio, with the amount of the amino group being 1.0.

The total amount of epoxy group, alkenyl group and acryloyl group contained in the adhesive component in the silicone rubber composition is 0.3 or more in terms of molar ratio, where 1.0 is the amount of hydrosilyl group contained in the cross-linking agent. It is preferably 2.3 or less.

The silicone rubber composition preferably contains an adhesive component having at least an epoxy group as an adhesive component.

The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less.

According to the fixing belt according to the present invention, the amount of hydrosilyl groups contained in the cross-linking agent of the silicone rubber composition forming the rubber elastic layer is equal to or less than the amount of alkenyl groups contained in the organopolysiloxane, and the primer composition. Since the adhesive component contained and the adhesive component contained in the silicone rubber composition each have a specific functional group, the adhesiveness between the metal layer and the primer layer and the adhesiveness between the primer layer and the rubber elastic body layer. Is improved, and peeling between the metal layer and the rubber elastic body layer is suppressed during durability.

At this time, when the amount of alkenyl groups in the primer composition is 0.8 or more and 3.0 or less in terms of molar ratio, where the amount of amino groups is 1.0, between the primer layer and the rubber elastic body layer. It has an excellent balance between the effect of improving the adhesiveness of the metal layer and the effect of improving the adhesiveness between the metal layer and the primer layer, and is more excellent in the adhesiveness between the metal layer and the rubber elastic body layer at the time of durability.

Further, the total amount of the epoxy group, the alkenyl group and the acryloyl group contained in the adhesive component in the silicone rubber composition is 0.3 or more in terms of molar ratio, where the amount of the hydrosilyl group contained in the cross-linking agent is 1.0. When it is 2.3 or less, it is excellent in the effect of improving the adhesiveness between the primer layer and the rubber elastic body layer, and is more excellent in the adhesiveness between the metal layer and the rubber elastic body layer at the time of durability.

Further, when the silicone rubber composition contains an adhesive component having at least an epoxy group as the adhesive component, it is excellent in suppressing deterioration of the characteristics of the rubber elastic body layer due to the addition of the adhesive component.

When the thickness of the primer layer 16 is 0.1 μm or more and 10 μm or less, the effect of improving the adhesiveness between the metal layer 14 and the rubber elastic body layer 18 is excellent, and the metal layer and the rubber elastic body are excellent in durability. Excellent adhesion between layers.

It is a schematic diagram of the fixing belt which concerns on one Embodiment of this invention. FIG. 5 is a cross-sectional view taken along the line AA of the fixing belt shown in FIG.

As shown in FIG. 1, the fixing belt 10 according to the embodiment of the present invention is formed on the base layer 12, the metal layer 14 formed on the outer peripheral surface of the base layer 12, and the outer peripheral surface of the metal layer 14. It has a primer layer 16 and a rubber elastic body layer 18 formed on the outer peripheral surface of the primer layer 16. The fixing belt 10 is formed in a cylindrical shape. The fixing belt 10 is a fixing belt for an electrophotographic device preferably used in a fixing process for an electrophotographic device such as a copying machine, a printer, or a facsimile.

The base layer 12 is the base of the fixing member 10. The base layer 12 is formed in a cylindrical shape and has a seamless structure having no joints in the circumferential direction. The base layer 12 is made of a material containing an organic polymer.

The organic polymer of the base layer 12 is preferably an organic polymer having excellent heat resistance. Examples of the organic polymer of the base layer 12 include polyamide-imide, modified polyamideimide, polyimide, modified polyimide, polyether sulfone, fluororesin, and polycarbonate. These may be used alone as the organic polymer of the base layer 12, or may be used in combination of two or more. Among these, polyamideimide, modified polyamideimide, polyimide, modified polyimide and the like are more preferable from the viewpoint of excellent rigidity and improvement in durability.

Additives and the like may be contained in the base layer 12. Examples of the additive include a mold release agent, a flame retardant, a filler, a leveling agent, an antifoaming agent and the like.

The thickness of the base layer 12 is not particularly limited, but is preferably in the range of 20 to 200 μm from the viewpoint of durability and manufacturability. It is more preferably in the range of 25 to 140 μm, and even more preferably in the range of 30 to 80 μm.

The metal layer 14 is a layer that functions as a heat generating layer that generates heat by electromagnetic induction heating. In the principle of heat generation by induction heating using an IH coil, when an AC current is supplied to an IH coil arranged in the vicinity of the fixing belt 10, a magnetic field is induced, and the magnetic field causes an eddy current in the metal layer 14 of the fixing belt 10. Is generated, and the metal layer 14 generates heat. The metal layer 14 is composed of at least one metal of copper, copper alloy, nickel, nickel alloy, silver, silver alloy, zinc, zinc alloy, tin, tin alloy, gold, and gold alloy. The metal layer 14 preferably contains at least copper and a copper alloy from the viewpoints of cost, heat generation, processability, and the like. The metal layer 14 may be a single layer or may be a multilayer of two or more layers. The multilayer metal layer 14 may be composed of two or more kinds of metals. The metal layer 14 can be formed by plating.

The thickness of the metal layer 14 is not particularly limited, but is preferably 3.0 μm or more from the viewpoint of heat generation and durability. It is more preferably 5.0 μm or more, still more preferably 10 μm or more. Further, from the viewpoint of durability and the like, 30 μm or less is preferable. It is more preferably 28 μm or less, still more preferably 25 μm or less.

A plating base layer may be provided below the metal layer 14 and above the base layer 12. The plating base layer serves as a base for forming the metal layer 14 by plating. The plating base layer contains at least the plating catalyst necessary for performing plating.

The primer layer 16 functions as a layer for improving the adhesiveness between the metal layer 14 and the rubber elastic body layer 18. The primer layer is composed of a cured product of a primer composition containing an adhesive component having an amino group and an adhesive component having an alkenyl group.

The adhesive component having an amino group in the primer composition has a function of suppressing the formation of an oxide film on the surface of the metal layer 14 on the primer layer 16 side. Examples of the adhesive component having an amino group include a silane coupling agent having an amino group, a silicone oligomer / polymer having an amino group, and the like. The adhesive component having an amino group preferably further has an alkoxy group from the viewpoint of improving the adhesiveness between the metal layer 14 and the primer layer 16.

The adhesive component having an alkenyl group in the primer composition is an adhesive component that improves the adhesiveness between the primer layer 16 and the rubber elastic body layer 18. Examples of the adhesive component having an alkenyl group include a silane coupling agent having an alkenyl group, a silicone oligomer / polymer having an alkenyl group, and the like. The adhesive component having an alkenyl group preferably further has an alkoxy group from the viewpoint of improving the adhesiveness between the metal layer 14 and the primer layer 16. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and the like. As the alkenyl group, a vinyl group is particularly preferable from the viewpoint of reactivity.

The amount of alkenyl groups in the primer composition is preferably 0.8 or more and 3.0 or less in terms of molar ratio, with the amount of amino groups being 1.0. When the molar ratio is 0.8 or more, a sufficient amount of alkenyl groups is secured, so that the effect of improving the adhesiveness between the primer layer 16 and the rubber elastic layer 18 is particularly excellent. From this point of view, the molar ratio is more preferably 1.0 or more. On the other hand, when the molar ratio is 3.0 or less, the amount of amino groups is sufficiently secured, so that the effect of improving the adhesiveness between the metal layer 14 and the primer layer 16 is particularly excellent. From this point of view, the molar ratio is more preferably 2.0 or less. When the molar ratio is 0.8 or more and 3.0 or less, the effect of improving the adhesiveness between the primer layer 16 and the rubber elastic body layer 18 and the effect between the metal layer 14 and the primer layer 16 are achieved. It is excellent in the balance of the effect of improving the adhesiveness, and is more excellent in the adhesiveness between the metal layer 14 and the rubber elastic body layer 16 at the time of durability.

The thickness of the primer layer 16 is preferably 0.1 μm or more and 10 μm or less. When the thickness of the primer layer 16 is 0.1 μm or more and 10 μm or less, the effect of improving the adhesiveness between the metal layer 14 and the rubber elastic body layer 18 is excellent. From this viewpoint, the thickness of the primer layer 16 is more preferably 0.3 μm or more and 5.0 μm or less, and further preferably 0.5 μm or more and 2.0 μm or less.

The rubber elastic body layer 18 is formed in a cylindrical shape on the primer layer 16 and has a seamless structure having no joints in the circumferential direction. Silicone rubber is used as the base material for the rubber elastic body layer 18. By elastically deforming the rubber elastic body layer 14, the nip width at the time of pressure contact with the pressure member is secured.

The rubber elastic layer 18 is at least one of an organopolysiloxane having an alkenyl group, a cross-linking agent having a hydrosilyl group, an adhesive component having an epoxy group, an adhesive component having an alkenyl group, and an adhesive component having an acryloyl group. It is composed of an adhesive component and a cured product of a silicone rubber composition containing.

The organopolysiloxane is an organopolysiloxane having at least two alkenyl groups in one molecule that are crosslinked by a cross-linking agent having a hydrosilyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and the like. Organopolysiloxane having an alkenyl group is used as a main raw material for an addition-curable silicone rubber composition. The organopolysiloxane having an alkenyl group is cross-linked by the cross-linking agent having a hydrosilyl group in an addition reaction with the cross-linking agent having a hydrosilyl group. This addition reaction proceeds even at room temperature, but is promoted under heating conditions. The temperature at which thermosetting by this addition reaction is carried out is usually more than 100 ° C., preferably in the range of 100 to 170 ° C. A platinum catalyst as a hydrosilylation catalyst (crosslinking catalyst) is preferably used for this addition reaction.

Organopolysiloxane has an organic group. The organic group is a monovalent or unsubstituted hydrocarbon group. The unsubstituted hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group, an aryl group such as a phenyl group, a β-phenylethyl group and a β-phenylpropyl group. Aralkill group of. Examples of the substituted hydrocarbon group include a chloromethyl group, a 3,3,3-trifluoropropyl group and the like. As the organopolysiloxane, those having a methyl group as an organic group are generally often used because of ease of synthesis and the like. The organopolysiloxane is preferably linear, but may be branched or cyclic.

A cross-linking agent having a hydrosilyl group is used as a cross-linking agent for an addition-curable silicone rubber composition. A cross-linking agent having a hydrosilyl group has a hydrosilyl group (SiH group) in its molecular structure. The cross-linking agent having a hydrosilyl group is an organopolysiloxane having a hydrosilyl group (organohydrogenpolysiloxane). The number of hydrosilyl groups in the molecular structure is not particularly limited, but is preferably in the range of 2 to 50 from the viewpoint of excellent curing rate, excellent stability, and the like. When there are two or more hydrosilyl groups in the molecular structure, the hydrosilyl groups are preferably present in different Sis. The polysiloxane may be chain-like or cyclic. The hydrosilyl group-containing organopolysiloxane preferably has at least two hydrosilyl groups in one molecule. The cross-linking agent having a hydrosilyl group is preferably in the range of a number average molecular weight of 200 to 30,000 from the viewpoint of excellent handleability and the like.

Specific examples of the organopolysiloxane having a hydrosilyl group (organohydrogenpolysiloxane) include a two-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane, and a two-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer. Both-terminal dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both-terminal dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends Trimethylsiloxy group-blocking methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, (CH ₃ ) ₂ HSiO 1/2 unit and SiO 4/2 unit copolymer, (CH ₃ ) ₂ HSiO 1/2 unit and SiO 4 Examples thereof include a copolymer composed of / 2 units and (C ₆ H _{5) SiO 3/2 units.}

The amount of hydrosilyl groups contained in the cross-linking agent in the silicone rubber composition is 0.3 or more and 1.0 or less in terms of molar ratio, where 1.0 is the amount of alkenyl groups contained in the organopolysiloxane. In this type of silicone rubber composition, the molar ratio is usually more than 1.0, particularly the molar ratio is 1.5 or more, in order to sufficiently crosslink the organopolysiloxane having an alkenyl group. In the present invention, the silicone rubber composition is blended with an adhesive component having a specific functional group. Therefore, when the molar ratio exceeds 1.0, the adhesive component internally added to the silicone rubber composition reacts with the cross-linking agent having a hydrosilyl group, and the amount of the adhesive component decreases. As a result, the above-mentioned adhesive component internally added to the silicone rubber composition cannot sufficiently exert the effect of improving the adhesiveness between the primer layer 16 and the metal layer 14 and the rubber elastic body layer 18. Insufficient sex. In the present invention, since the amount of the cross-linking agent having a hydrosilyl group is relatively small, the adhesive component internally added to the silicone rubber composition reacts with the cross-linking agent having a hydrosilyl group, and the amount of the adhesive component is reduced. Is suppressed. From this viewpoint, the molar ratio is more preferably 0.9 or less, still more preferably 0.8 or less. On the other hand, from the viewpoint of ensuring the crosslink density of the base organopolysiloxane, the molar ratio is more preferably 0.4 or more, still more preferably 0.5 or more.

The adhesive component (internal adhesive component) contained in the silicone rubber composition improves the adhesiveness between the primer layer 16 and the rubber elastic body layer 18. The internal adhesive component is at least one of an epoxy group-containing adhesive component, an alkenyl group-containing adhesive component, and an acryloyl group-containing adhesive component. The internal adhesive component may be composed of one of these, or may be composed of two or more. Among these, the adhesive component having an epoxy group and the adhesive component having an alkenyl group are more preferable as the internal adhesive component from the viewpoint of excellent cross-linking speed and the like. Further, from the viewpoint of excellent suppression of deterioration of hardness and strength of the rubber elastic body layer 18 due to the addition of the internal adhesive, it is preferable to contain at least an adhesive component having an epoxy group.

Examples of the adhesive component having an epoxy group include a silane coupling agent having an epoxy group, a silicone oligomer / polymer having an epoxy group, and the like. The adhesive component having an epoxy group may further have an alkoxy group. Examples of the adhesive component having an alkenyl group include a silane coupling agent having an alkenyl group, a silicone oligomer / polymer having an alkenyl group, and the like. The adhesive component having an alkenyl group may further have an alkoxy group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and the like. As the alkenyl group, a vinyl group is particularly preferable from the viewpoint of reactivity. Examples of the adhesive component having an acryloyl group include a silane coupling agent having an acryloyl group, a silicone oligomer / polymer having an acryloyl group, and the like. The adhesive component having an acryloyl group may further have an alkoxy group.

The total amount of epoxy group, alkenyl group and acryloyl group contained in the adhesive component in the silicone rubber composition is 0.3 or more in terms of molar ratio, where 1.0 is the amount of hydrosilyl group contained in the cross-linking agent. It is preferably 3 or less. When the molar ratio is within a specific range, the effect of improving the adhesiveness between the primer layer and the rubber elastic body layer is excellent, and the effect of suppressing peeling between the metal layer and the rubber elastic body layer during durability is excellent. Better. From this viewpoint, the molar ratio is more preferably 0.5 or more and 2.0 or less, still more preferably 0.5 or more and 1.5 or less.

The cross-linking catalyst is a catalyst that promotes the cross-linking reaction of organopolysiloxane with a cross-linking agent. Examples of the cross-linking catalyst include a platinum catalyst as a hydrosilylation catalyst, a ruthenium catalyst, and a rhodium catalyst. Examples of the platinum catalyst include fine particle platinum, platinum black, platinum-supported activated carbon, platinum-supported silica, platinum chloride acid, alcohol solution of platinum chloride acid, an olefin complex of platinum, and an alkenylsiloxane complex of platinum. These may be used alone or in combination of two or more.

The blending amount of the cross-linking catalyst is not particularly limited, but is usually in the range of 1 ppm to 1.0 part by mass with respect to 100 parts by mass of the organopolysiloxane in terms of the amount of metal.

In addition to the above-mentioned organopolysiloxane, the above-mentioned cross-linking agent, and the above-mentioned adhesive component having a specific functional group, the silicone rubber composition includes, if necessary, a filler, a cross-linking accelerator, and a cross-linking delay as long as the present invention is not impaired. Additives such as agents, cross-linking aids, scorch inhibitors, anti-aging agents, softeners, heat stabilizers, flame retardants, flame retardants, UV absorbers, rust preventives, conductive agents, antistatic agents, etc. are added. You may be. Examples of the filler include reinforcing fillers such as fumed silica, crystalline silica, wet silica, and fumed titanium oxide. Further, a heat conductive filler for increasing the heat conductivity may be added.

The thickness of the rubber elastic body layer 18 is not particularly limited, but is preferably in the range of 100 to 400 μm. More preferably, it is in the range of 150 to 300 μm.

The fixing belt 10 can be manufactured as follows.

First, the base layer 12 is formed. The base layer 12 is formed by using a base layer forming material containing an organic polymer. Specifically, a base layer forming material (paint) is applied to the outer peripheral surface of a cylindrical or columnar mold and dried. If necessary, heat treatment may be performed. Examples of the coating method include a dip coating method, a dispenser coating method (nozzle coating method), a roll coating method, and a ring coating method.

Next, the metal layer 14 is formed on the outer peripheral surface of the base layer 12. The metal layer 14 can be formed by plating. A plating base layer may be formed on the outer peripheral surface of the base layer 12 that forms the metal layer 14. The plating base layer serves as a base for forming the metal layer 14 by plating. The plating base layer contains at least the plating catalyst necessary for performing plating. The plating base layer can be formed by using a base forming material (paint) containing a plating catalyst and a binder. The applied base forming material (paint) may be dried or heat-treated, if necessary. Further, after application, degreasing treatment, cleaning treatment and the like may be performed. The plating base layer is a coating film containing a plating catalyst and a binder.

The plating catalyst may be any catalyst having the catalytic ability required for plating on the plating base layer. Examples of such a catalyst metal include Pt group metals such as Pd and Pt, Ag, Au, and alloys thereof. These may be used alone as a catalyst metal for plating, or may be used in combination of two or more. Among these, Pd, Pt, Ag, and alloys thereof are more preferable from the viewpoint of being more excellent in catalytic ability. Further, Pd is particularly preferable.

Examples of the binder include polyimide, polyamide-imide, modified polyamideimide, modified polyimide, polyether sulfone, fluororesin, polycarbonate and the like.

In the base forming material (paint), the solid content concentration of the plating catalyst is preferably 0.1% by mass or more from the viewpoint of plating efficiency and the like. More preferably, it is 0.5% by mass or more. Further, from the viewpoint of dispersibility of the plating catalyst, adhesion of the metal layer 14, and the like, it is preferably 10.0% by mass or less. More preferably, it is 6.0% by mass or less.

The thickness of the plating base layer is not particularly limited, but is preferably 0.05 μm or more from the viewpoint of adhesion to the base layer 12 and the metal layer 14 and uniformity. It is more preferably 0.1 μm or more, still more preferably 0.3 μm or more. Further, from the viewpoint of economy and the like, it is preferably 10 μm or less. It is more preferably 5.0 μm or less, still more preferably 3.0 μm or less.

Next, plating is performed to form a metal layer 14 on the plating base layer. The metal layer 14 can be formed by electroless metal plating or electrolytic plating. Electroless metal plating and electrolytic plating are performed using a plating solution. If necessary, it may be washed with water or the like after plating.

The plating solution contains metal ions, a reducing agent, a complexing agent, a pH buffer, and the like. The metal ion is an ion of a plated metal. Examples of the plating metal include Cu, Ni, Ag, Pd, Sn, Au, and alloys thereof. Of these, Cu, Ni, and alloys thereof are more preferable from the viewpoint of excellent adhesion to the plating base.

Examples of the reducing agent include hypophosphorous acid, hypophosphite, dimethylamine borane, hydrazine and the like. Of these, hypophosphorous acid and hypophosphate are preferable from the viewpoint of stability of the plating solution and the like. Examples of the pH buffer include lactic acid, acetic acid, and succinic acid.

Examples of the complexing agent include carboxylic acids and amine compounds. As the complexing agent, only the carboxylic acid may be used, only the amine compound may be used, or the carboxylic acid and the amine compound may be used in combination. Examples of the carboxylic acid include citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA) and the like. Examples of the amine compound include glycine, alanine, ethylenediamine, propanediamine and the like.

A surfactant may be further added to the plating solution. Examples of the surfactant include a cationic surfactant and an amphoteric surfactant.

Examples of the cationic surfactant include quaternary ammonium salt types such as lauryltrimethylammonium chloride and ethylene oxide-added ammonium chloride. These may be used alone or in combination. Examples of amphoteric surfactants include betaine-type surfactants such as lauryl betaine, amide propyl betaine, and dimethyl alkyl betaine. These may be used alone or in combination. The blending amount of the cationic surfactant or the blending amount of the amphoteric surfactant is preferably in the range of 0.01 to 10 g / L.

Next, the primer composition is applied onto the outer peripheral surface of the metal layer 14. Examples of the coating method include a dip coating method, a spray coating method, and a brush coating method. The primer composition may be diluted with a diluent. As the diluent, a solvent capable of dissolving or dispersing the adhesive component may be used. Examples of such a solvent include alcohols and ketones. The applied primer composition may be dried, if necessary. However, the cross-linking / curing treatment of the primer composition is performed together with the cross-linking / curing treatment of the silicone rubber composition after the silicone rubber composition is applied.

Next, the silicone rubber composition is coated on the outer peripheral surface of the coated primer composition. Examples of the coating method include a dip coating method. Next, the coated primer composition and the silicone rubber composition are crosslinked and cured. As a result, the primer layer 16 is formed on the outer peripheral surface of the metal layer 14, and the rubber elastic body layer 18 is formed on the outer peripheral surface of the primer layer 16. As described above, the fixing belt 10 is manufactured.

According to the fixing belt 10 having the above configuration, the amount of hydrosilyl groups contained in the cross-linking agent of the silicone rubber composition forming the rubber elastic layer 18 is equal to or less than the amount of alkenyl groups contained in the organopolysiloxane, and the primer composition. Since the adhesive component contained in the product and the adhesive component contained in the silicone rubber composition each have a specific functional group, the adhesiveness between the metal layer 14 and the primer layer 16 and the adhesion between the primer layer 16 and the rubber elastic body layer 18 are achieved. The adhesiveness between the metal layer 14 and the rubber elastic body layer 18 is suppressed during durability.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

For example, a surface layer may be further provided on the rubber elastic body layer 18. By providing the surface layer, adhesion of toner is further suppressed. Examples of the surface layer material include fluororesins and fluororubbers. The thickness of the surface layer is not particularly limited, but is preferably 5.0 μm or more from the viewpoint of durability and the like. Further, from the viewpoint of thermal conductivity and the like, 100 μm or less is preferable.

The surface of the rubber elastic body layer 18 may be modified instead of forming the surface layer. Examples of the surface modification include fluorine modification and ultraviolet irradiation. The surface modification further suppresses the adhesion of toner as well as the formation of the surface layer.

The fixing belt 10 is configured to be heated by self-heating using induction heating, but may be configured to be heated from another heat source.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

(Examples 1 to 7, 12 to 15)
<Material for forming the base layer>
Toyobo Polyamide-imide varnish "Vilomax HR-16NN (solid content 14.0%)" was prepared.

<Paint for forming plating base>
Iox's "Metalloid" was prepared as a paint for forming a plating base. The viscosity of the liquid is 80 mPa · s.

<Solvent degreasing liquid>
A degreasing liquid was prepared by mixing 200 ml of an alkaline degreasing agent (manufactured by Okuno Pharmaceutical Co., Ltd., "OPC-190 cleaner"), 1200 ml of 3% by mass caustic soda, and 600 ml of ion-exchanged water.

<Electroless nickel plating solution>
By mixing nickel sulfate hexahydrate: 26 g / L, sodium hypophosphate monohydrate (reducing agent): 32 g / L, sodium citrate dihydrate (complexing agent): 30 g / L. , Electroless nickel plating solution.

<Electrolytic copper plating solution>
An electrolytic copper plating solution was prepared by mixing 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 5 ml / L of brightener [“Top Lucina LS” manufactured by Okuno Pharmaceutical Co., Ltd.], and 0.125 ml / L of 35% hydrochloric acid.

<Preparation of primer composition>
Amino-based adhesive component (amino-based silane coupling agent: "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.) and vinyl-based adhesive component (vinyl-based silane coupling agent: Shin-Etsu Chemical Co., Ltd.) with the compounding composition (part by mass) shown in the table. The primer composition was prepared by mixing with "KBM-1003" manufactured by Japan, and diluting with methanol at a solid content concentration of 5% by mass.

<Preparation of silicone rubber composition>
With the compounding composition (parts by mass) shown in the table, 3% by mass IPA of a platinum catalyst (fluyametal platinum (IV) chloride (IV) acid hydrate) with respect to vinyl group-containing dimethylpolysiloxane (“DMS-V35” manufactured by Gelest). After blending the solution), mix with a planetary mixer for 30 minutes, then a hydrosilyl group-containing cross-linking agent (“KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd., hydrosilyl group-containing dimethylpolysiloxane), a retarder (1-ethynyl-1). -Cyclohexanol) and an epoxy-based adhesive component (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., an epoxy-based silane coupling agent) were blended and then mixed for another 30 minutes to prepare a silicone rubber composition.

<Material for forming an adhesive layer>
A stock solution of one-component RTV rubber (“KE-3417” manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a material for forming an adhesive layer.

<Material for surface layer formation>
As a material for forming the surface layer, a tube (thickness 30 μm) made of a tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA) was prepared.

<Preparation of base layer>
A base layer forming material was applied to the surface of an aluminum cylindrical pipe having a diameter of 40 mm and an axial length of 450 mm by a dip coating method, and dried at 230 ° C. for 60 minutes. The pulling speed at the time of the above coating was set to 100 mm / sec. As a result, a tubular base layer (thickness 80 μm) made of polyamide-imide (PAI) was formed on the outer peripheral surface of the cylindrical pipe.

<Formation of metal layer>
A coating material for forming a plating base was applied onto the outer peripheral surface of the base layer, heat-treated at 120 ° C. for 15 minutes, and then further heat-treated at 240 ° C. for 15 minutes. As a result, a plating base layer (thickness 0.5 μm) was formed on the outer peripheral surface of the base layer. Then, it was immersed in a degreasing solution at 65 ° C. for 5 minutes, and then washed with water by pouring pure water over it. Then, it was immersed in an electroless nickel plating solution (plating solution temperature: 84 ° C., plating time: 2 minutes), and then washed with water by pouring pure water over it. As a result, an electroless nickel plating layer (thickness 1.0 μm) was formed on the outer peripheral surface of the plating base layer. Next, electrolytic copper plating was performed on the surface of the electroless nickel plating layer using an electrolytic copper plating solution to form an electrolytic copper plating layer (thickness 20 μm) (plating solution temperature: 25 ° C., current density: 2.3 A). / Dm ² , plating time: 40 minutes). As described above, a metal layer was formed on the outer peripheral surface of the base layer.

<Formation of primer layer and rubber elastic layer>
After applying the primer composition on the outer peripheral surface of the metal layer and drying it, the silicone rubber composition is applied on the outer peripheral surface of the primer composition and heat-treated at 130 ° C. for 30 minutes to obtain the metal layer. A rubber elastic body layer (thickness 200 μm) was formed on the outer peripheral surface via a primer layer.

<Formation of surface layer>
After applying the adhesive layer forming material to the surface of the rubber elastic body layer, a tubular surface layer forming material was covered. As a result, a surface layer (thickness 30 μm) made of fluororesin was formed on the outer peripheral surface of the rubber elastic body layer. From the above, a fixing belt was produced.

(Examples 8-9, 16-17)
A fixing belt was produced in the same manner as in Example 3 except that the thickness of the primer layer was changed.

(Examples 10 to 11)
A fixing belt was produced in the same manner as in Example 2 except that the internal adhesive component was changed in the preparation of the silicone rubber composition.
-Vinyl adhesive component (vinyl silane coupling agent: "KBM-1403" manufactured by Shin-Etsu Chemical Co., Ltd.)
-Acrylic adhesive component (Acrylic silane coupling agent: "NK Oligo EA-1010N" manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

(Comparative Examples 1 to 3)
No internal adhesive component was added in the preparation of the silicone rubber composition. Further, in the preparation of the primer composition, neither the amino-based adhesive component nor the vinyl-based adhesive component was blended. A fixing belt was produced in the same manner as in Example 3 except for this.

(Comparative Example 4)
No internal adhesive component was added in the preparation of the silicone rubber composition. A fixing belt was produced in the same manner as in Example 3 except for this.

(Comparative Example 5)
In the preparation of the silicone rubber composition, the internal adhesive component was changed. A fixing belt was produced in the same manner as in Example 3 except for this.
-Mercapt-based adhesive component: "KBM-803" manufactured by Shin-Etsu Chemical Co., Ltd.

(Comparative Example 6)
In the silicone rubber composition, the molar ratio of hydrosilyl groups is high. Along with this, the amount of the epoxy-based adhesive component has increased. A fixing belt was produced in the same manner as in Example 3 except for this.

(Comparative Example 7)
In the silicone rubber composition, the molar ratio of hydrosilyl groups is low. Along with this, the amount of the epoxy-based adhesive component has decreased. A fixing belt was produced in the same manner as in Example 3 except for this.

(Comparative Examples 8 to 10)
In the preparation of the primer composition, neither the amino-based adhesive component nor the vinyl-based adhesive component was blended. A fixing belt was produced in the same manner as in Example 3 except for this.

(Evaluation of adhesiveness)
From the prepared fixing belt, strip-shaped test pieces having a length of 10 cm and a width of 1 cm were collected. Then, using a utility knife, a cut was made at the interface between the rubber elastic layer and the metal layer. Next, a tensile tester (“Precision universal tester AGS-1kNX” manufactured by Shimadzu Corporation) was used to perform a 180 ° peel test so as to peel off the upper layer and the lower layer separated by the notch (tensile speed 25 mm / min). A peel test was performed before heating (initial stage) and after heating (220 ° C. for 1 week) (after durability). When the peel strength was 2.0 N / cm or more, it was "A", and the peel strength was 0.5 N. When it was / cm or more and less than 2.0 N / cm, it was designated as "B", and when the peel strength was less than 0.5 N / cm, it was designated as "C".

In Comparative Examples 1 to 4, the silicone rubber composition forming the rubber elastic layer does not contain a specific adhesive component. Therefore, the adhesiveness between the primer layer and the rubber elastic body layer is insufficient, and the adhesiveness at the initial stage and the durability is not satisfied. In Comparative Example 5, the silicone rubber composition forming the rubber elastic layer contains a mercapto-based adhesive component instead of a specific adhesive component. Therefore, the adhesiveness between the primer layer and the rubber elastic body layer is insufficient, and the adhesiveness at the initial stage and the durability is not satisfied. In Comparative Example 6, the amount of the cross-linking agent having a hydrosilyl group is too large. For this reason, a specific adhesive component contained in the silicone rubber composition forming the rubber elastic body layer reacts with the cross-linking agent, and the effect of improving the adhesiveness between the primer layer and the rubber elastic body layer is reduced. , The adhesiveness between the primer layer and the rubber elastic layer is insufficient, and the adhesiveness at the initial stage and the durability is not satisfied. In Comparative Example 7, the amount of the cross-linking agent having a hydrosilyl group is too small. Therefore, the rubber elastic layer could not be molded, and the adhesiveness could not be evaluated. In Comparative Examples 8 to 10, the primer composition does not contain two specific adhesive components. Therefore, the adhesiveness between the primer layer and the metal layer or the adhesiveness between the primer layer and the rubber elastic body layer is insufficient, and the adhesiveness at the initial stage and the durability is not satisfied.

For each comparative example, in the examples, the primer composition contains two specific adhesive components, and the silicone rubber composition forming the rubber elastic layer contains a specific adhesive component, and further, hydrosilyl. The blending amount of the cross-linking agent having a group is within a specific range. Therefore, the adhesiveness between the primer layer and the metal layer and the adhesiveness between the primer layer and the rubber elastic body layer are improved, and the adhesiveness at the initial stage and during durability is excellent.

Then, from the comparison between the examples, when the amount of the alkenyl group in the primer composition is 0.8 or more and 3.0 or less in terms of molar ratio, where the amount of the amino group is 1.0, the primer layer and the metal The adhesiveness between the layers and the primer layer and the rubber elastic layer are improved, and the adhesiveness at the initial stage and during durability is superior (Examples 4, 5, 14 and 15). Further, the total amount of the epoxy group, the alkenyl group and the acryloyl group contained in the adhesive component in the silicone rubber composition is 0.3 or more in terms of molar ratio, where the amount of the hydrosilyl group contained in the cross-linking agent is 1.0. When it is 2.3 or less, the adhesiveness between the primer layer and the rubber elastic body layer is improved, and the adhesiveness at the initial stage and the durability is excellent (Examples 6, 7, 12, 13). Further, when the thickness of the primer layer is 0.1 μm or more and 10 μm or less, the effect of improving the adhesiveness between the metal layer and the rubber elastic body layer is excellent, and the adhesiveness at the initial stage and the durability is excellent (Example). 8, 9, 16, 17).

Although the examples of the present invention have been described above, the present invention is not limited to the above examples, and various modifications can be made without departing from the spirit of the present invention.

10 Fixing belt 12 Base layer 14 Metal layer 16 Primer layer 18 Rubber elastic layer

Claims (5)

A tubular base layer, a metal layer formed on the outer peripheral surface of the base layer, a primer layer formed on the outer peripheral surface of the metal layer, and a rubber elastic body layer formed on the outer peripheral surface of the primer layer. And, which is a fixing belt for electrophotographic equipment.
The metal layer is composed of at least one metal of copper, copper alloy, nickel, nickel alloy, silver, silver alloy, zinc, zinc alloy, tin, tin alloy, gold and gold alloy.
The primer layer is composed of a cured product of a primer composition containing an adhesive component having an amino group and an adhesive component having an alkenyl group.
The rubber elastic layer is at least one of an organopolysiloxane having an alkenyl group, a cross-linking agent having a hydrosilyl group, an adhesive component having an epoxy group, an adhesive component having an alkenyl group, and an adhesive component having an acryloyl group. Consists of an adhesive component and a cured product of a silicone rubber composition containing
The amount of hydrosilyl groups contained in the cross-linking agent in the silicone rubber composition is 0.3 or more and 1.0 or less in terms of molar ratio, where 1.0 is the amount of alkenyl groups contained in the organopolysiloxane. A fixing belt that is characterized by that. The fixation according to claim 1, wherein the amount of the alkenyl group in the primer composition is 0.8 or more and 3.0 or less in terms of molar ratio, where 1.0 is the amount of the amino group. belt. The total amount of epoxy group, alkenyl group and acryloyl group contained in the adhesive component in the silicone rubber composition is 0.3 or more in terms of molar ratio, where 1.0 is the amount of hydrosilyl group contained in the cross-linking agent. The fixing belt according to claim 1 or 2, wherein the fixing belt is 2.3 or less. The fixing belt according to any one of claims 1 to 3, wherein the silicone rubber composition contains an adhesive component having at least an epoxy group as an adhesive component. The fixing belt according to any one of claims 1 to 4, wherein the thickness of the primer layer is 0.1 μm or more and 10 μm or less.

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