JP5907775B2 - Heating member - Google Patents

Description

  The present invention relates to a heating member.

  Conventionally, in various fields, a heating member has been used to heat an object to be heated. For example, an image forming apparatus such as a copying machine or a printer that employs an electrophotographic method generally undergoes each process of latent image formation by image data exposure to a charged photoreceptor, development, transfer to a transfer medium, and fixing. Perform image formation. In the fixing step, a heating member such as a heating belt or a heating roller is used to form an image by melting and fixing the toner transferred to the transfer material (paper) by heating.

  Known heating members include halogen heaters and ceramic heaters. Recently, an electromagnetic induction heating (hereinafter, sometimes abbreviated as IH) heating member has attracted attention. This is because the IH heating member is advantageous in reducing power consumption by shortening the warm-up time. This type of heating member has a conductive layer that generates an induced current by electromagnetic induction heating, and uses the conductive layer as a heat generating layer. A metal plating layer is generally used as the conductive layer.

  As the heating member, for example, Patent Document 1 discloses a heating member having an electroless nickel plating layer, an electrolytic copper plating layer, and a silicone rubber layer on a base layer made of polyimide resin.

JP 2009-25565 A

However, the conventional heating member has problems in the following points.
That is, in order to form a heating member having the above-mentioned metal plating layer, usually, a catalyst metal precursor such as Pd is applied to the surface of a polymer base layer, and then the precursor is metallized by reduction. Process. Then, after such a plating pretreatment step for the base layer, an electroless metal plating layer is formed on the surface of the base layer. Furthermore, an electrolytic metal plating layer is formed using this as an electrode.

  However, the electroless metal plating layer formed by performing the plating pretreatment has poor adhesion to the base layer. Therefore, the electroless metal plating layer is easily peeled from the base layer. Moreover, if the electroless metal plating layer peels from the base layer, as a result, the electrolytic metal plating layer or the like laminated thereon also peels from the base layer. That is, the heating member has a problem that the adhesion between the base layer and the metal plating layer is inferior. If the metal plating layer is peeled off from the base layer during use of the heating member, temperature rise due to electromagnetic induction heating is reduced. The heating member is usually not used on the premise of regular replacement but is used repeatedly. Therefore, having durability is particularly important.

  This invention is made | formed in view of the said background, and is providing the heating member excellent in the adhesiveness of a base layer and a metal plating layer.

One aspect of the present invention is a heating member for heating an object to be heated,
A base layer made of a polymer for the base layer, a plating base layer laminated on the base layer, and a first metal plating layer laminated on the plating base layer and formed by electroless metal plating; ,
The plating base layer has a portion in which a catalyst-supporting carrier supporting a catalyst metal is dispersed on the surface of the carrier in a binder polymer, and the catalyst-supporting carrier is exposed on the surface of the first metal plating layer. And
The binder polymer, Ru heating member near characterized by one or more der Rukoto polyamideimide resin, a modified polyamide-imide resin and these resins polysiloxane compound is selected from those blends.

  In the heating member, the plating underlayer is formed by dispersing a catalyst-carrying carrier carrying a catalyst metal on the carrier surface in a binder polymer. Therefore, the base layer polymer and the binder polymer, that is, the polymers are in close contact with each other between the base layer and the plating base layer. Therefore, the adhesion between the base layer and the plating base layer can be improved.

  In the heating member, the plating base layer has a portion where the catalyst-supporting carrier is exposed on the surface on the first metal plating layer side. And at the time of plating formation of the first metal plating layer, since the electroless metal plating is deposited with the catalyst metal of the catalyst-supporting carrier exposed on the surface of the plating base layer as a nucleus, between the catalyst metal and the electroless metal plating, Bonded by metal bonds. Moreover, the part which is not exposed to the surface among the catalyst support | carriers exposed on the surface of the plating base layer is being fixed to the binder polymer. Therefore, the adhesion between the plating base layer and the first metal plating layer can be improved. In addition, even when electrolytic metal plating or electroless metal plating is further applied on the first metal plating layer and the metal plating layers are laminated, the plating layers are in close contact with each other, thus ensuring good adhesion. can do.

  Therefore, according to this invention, the heating member excellent in the adhesiveness of a base layer and a metal plating layer can be provided. Further, the heating member does not need to perform a complicated plating pretreatment process on the base layer at the time of manufacture. Therefore, it is possible to contribute to the downsizing of the production line, and the productivity is excellent.

1 is an external perspective view schematically showing a heating member of Example 1. FIG. It is II-II sectional drawing of FIG. It is explanatory drawing which expanded a part of FIG. 2, and showed typically the microstructure and laminated structure of the plating base layer. 6 is an explanatory view schematically showing a microstructure and a laminated structure of a plating underlayer in the heating member of Example 2. FIG. It is explanatory drawing which showed typically the outline | summary of the evaluation apparatus for evaluating the durability by electromagnetic induction heating about the heating member of a sample. It is a scanning electron micrograph (magnification 30,000 times) of Pd carrying carbon produced in the example of an experiment. It is a scanning electron micrograph (magnification 200,000 times) of Pd carrying carbon produced in the experiment example.

  The said heating member is used in order to heat a to-be-heated body. The kind of to-be-heated body is not specifically limited. Specifically, as the heated body, for example, unfixed toner transferred onto a transfer material such as paper, a plate, such as a gas, liquid, solid, or plate in a container, container or pipe, A film etc. can be illustrated. The heating member can be used in contact with the heated body or can be used in non-contact with the heated body.

  Moreover, a heating member can also be used in the state which pressed the surface to the other member. In this case, for example, the heated body can be heated while passing the heated body through the pressure contact portion between the heating member and the other member. Moreover, the said other member can also be used as a to-be-heated body. In these cases, an external force acts on the heating member during use, but the heating member is excellent in adhesion between the base layer and the metal plating layer, and is not easily peeled off. It can be demonstrated. In particular, when the heating member is configured to rotate in a state where the heating member and the other member are in pressure contact, the heating member is repeatedly deformed by receiving external force at the pressure contact portion. Even in such a case, the adhesiveness between the base layer and the metal plating layer is excellent, peeling or the like hardly occurs, and good durability can be exhibited.

  In the heating member, the base layer can be formed in a cylindrical shape, for example. In this case, the heating member can be used as a heating belt. Further, since the heating member can be made relatively thin, it is advantageous for improving the IH temperature rise performance. In addition, for example, the base layer can be formed in a roll shape on the outer periphery of the shaft body. In this case, the heating member can be used as a heating roll. The base layer can be composed of one layer or two or more layers.

  In the case of having a cylindrical base layer, the base layer polymer used for the base layer is, for example, a polyamideimide resin, a modified polyamideimide resin, a polyimide resin, a modified polyimide resin, a polyethersulfone resin, a fluorine resin, a polycarbonate resin, or these resins Examples thereof include those blended with a polysiloxane compound. These can be used alone or in combination of two or more. The base layer polymer preferably contains one or more selected from a polyamideimide resin, a modified polyamideimide resin, a polyimide resin, a modified polyimide resin, and a blend of these resins with a polysiloxane compound. Good. This is because the rigidity of the cylindrical base layer is high, which is advantageous for improving the durability of the heating member.

  As the polysiloxane compound, a silicone oil having a repeating structure represented by Formula 1 can be suitably used. In this case, it becomes easy to improve the bending durability and toughness of the heating member. This is because an island phase made of a polysiloxane compound is microdispersed in a sea phase made of a resin such as the above-mentioned polyamideimide resin, and it becomes easy to form a sea-island structure. This is thought to be mitigated. The blend amount of the polysiloxane compound is preferably about 0.01 to 10 parts by mass, and more preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin. This is because the heating member has an excellent balance of bending durability and toughness.

However, in Formula 1, R < ¹ > and R < ² > show a hydrogen atom or an organic group, respectively. N represents a positive number.

In the above formula 1, the organic group represented by R ¹ and R ² is not particularly limited, and examples thereof include an alkyl group such as a methyl group and an ethyl group, a phenyl group, an amino group, an epoxy group, a carboxyl group, and an alkoxy group. Group, ether group and the like. The repeating unit n in the above formula 1 is not particularly limited as long as it is a positive number, but preferably n = 10 to 1,000, and particularly preferably n = 20 to 300. The silicone oil is not particularly limited, but from the viewpoint of cost, a straight silicone oil bonded with a methyl group, a phenyl group, a hydrogen atom or the like as a substituent can be suitably used.

  In addition, 1 type, or 2 or more types of additives, such as a flame retardant, a filler, a leveling agent, and an antifoamer, can be contained in a cylindrical base layer. In addition, the thickness of the cylindrical base layer is preferably 20 to 200 μm, more preferably 40 to 150 μm, and still more preferably about 60 to 100 μm, from the viewpoints of improved durability and ease of manufacture.

  On the other hand, in the case of having a roll-shaped base layer, as the base layer polymer used for the base layer, various resins and rubbers (the rubber referred to in the present application includes an elastomer and is omitted below) can be used. Examples of the resin include urethane resin, urethane silicone resin, polyamide resin, polyimide resin, (meth) acrylic resin, (meth) acrylic silicone resin, fluororesin, acetal resin, alkyd resin, polyester resin, polyether resin, and carbonate. Resins, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulosic resins, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and Copolymers with these copolymers, polyethylene, polypropylene and other olefinic monomers Olefin resins, vinyl chloride resins, styrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, polyvinyl acetal resins such as vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, and derivatives or modified products thereof, Polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, Examples include polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof, melamine resins, and the like. Examples of the rubber include silicone rubber (Q), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), chloroprene rubber (CR), hydrin rubber ( Examples thereof include ECO, CO), isoprene rubber (IR), urethane rubber (U), ethylene-propylene-diene rubber (EPDM), and natural rubber (NR). These can be used alone or in combination of two or more.

  The roll-shaped base layer may contain one or more additives such as a flame retardant, a filler, a crosslinking agent, a crosslinking assistant, a lubricant, a plasticizer, a softening agent, and an antioxidant. The thickness of the roll-shaped base layer is preferably about 0.5 to 3 mm, more preferably about 1 to 1.5 mm, from the viewpoint of grounding property, cost, and the like.

  In the heating member, the plating underlayer is an important layer for improving the adhesion between the base layer and the first metal plating layer. The plating base layer is laminated on the base layer. Specifically, the plating base layer can be formed along the outer peripheral surface of the base layer.

  The plating underlayer is formed by dispersing a catalyst-carrying carrier carrying a catalyst metal on the carrier surface in a binder polymer. The binder polymer mainly has a role of holding the catalyst support in a dispersed state and forming a plating underlayer.

As the binder polymer, one or more selected from polyamideimide resins, modified polyamideimide resins, and those obtained by blending a polysiloxane compound with these resins are used.

In the heating member, the base layer polymer and the binder polymer, have good as containing polymers of the same kind. In this case, the affinity between the base layer and the plating base layer is increased, and the adhesion between the base layer and the plating base layer is easily improved. Preferably, the base layer polymer and the binder polymer are the same type of polymer. The “same type” means not only the case where the polymers are exactly the same, but also the case where the polymers have the same basic skeleton. Therefore, for example, it can be said that various resins classified into a certain type of resin (polyamideimide resin or the like) are the same type of polymer . Also, unmodified polymer and the modified polymer together, different molecular weight between polymers, polymers with each other such polymerized units are also common, it is included in the concept of the same type of polymer.

When using a polymer of the same type, as the base polymer, a polyamide-imide resin, modified polyamide-imide resin, it can be preferably used in a blend of the polysiloxane compound in these resins. This is because there are advantages such as excellent strength, heat resistance and flexibility in the case of a cylindrical shape (belt shape). On the other hand, as the binder polymer, a polyamide-imide resin, modified polyamide-imide resin, it can be preferably used in a blend of the polysiloxane compound in these resins. This is because there are advantages such as affinity with the polymer for the base layer, affinity with a carrier made of a carbon-based material described later, and excellent heat resistance.

The carrier constituting the catalyst-carrying carrier can have various particle shapes such as a spherical shape, a substantially spherical shape, a fiber shape, a columnar shape, a lump shape, and a substantially tufted shape. The material for the carrier, for example, carbon-based materials, metal oxides, and it is Ru can be with one or more selected from silica. In this case, it is easy to ensure affinity with the binder polymer, and it is easy to contribute to improvement in adhesion.

  Specific examples of the carbon-based material include carbon black, carbon nanotube, fullerene, and graphite. Specific examples of the metal oxide include titanium oxide, zinc oxide, aluminum oxide, and magnesium oxide. The material of the carrier is preferably a carbon-based material from the viewpoint of affinity with the binder polymer. Carbon black is particularly preferable from the viewpoints of ease of supporting the catalyst metal, affinity with the binder polymer, economy, and the like.

  The average particle diameter of the carrier is preferably about 0.01 to 10 μm, more preferably from the viewpoint of good dispersibility in the binder polymer and easy to ensure the smoothness of the plating base layer surface. The thickness can be about 0.05 to 5 μm, more preferably about 0.1 to 2 μm. The average particle size of the carrier can be measured by a laser diffraction / scattering particle size / particle size distribution measuring apparatus [manufactured by Nikkiso Co., Ltd., “Microtrack UPA-EX150”, etc.].

On the other hand, the catalyst metal that constitutes the catalyst-supporting carrier is a metal having a catalytic ability necessary to develop an electroless metal plating reaction (in the present application, the metal includes an alloy, and is omitted hereinafter). Examples of the catalyst metal include Pt group other than Pd, Pt, and Pt, Ag, Au, and alloys thereof. The catalyst metal, specifically, from the viewpoint of excellent catalytic ability, Pd, Pt, Ru can be one or more selected from Ag and their alloys. Among these, Pd can be used particularly preferably from the viewpoints of excellent catalytic ability and metal bonding with electroless metal plating, and high versatility.

Specifically, the catalyst-carrying carrier can have a structure in which an exposed portion where the carrier surface is exposed and a carrier portion where a catalyst metal is carried are mixed. In this case, it becomes easy to fix the catalyst-supporting carrier to the binder polymer by utilizing the affinity between the carrier surface and the binder. Therefore, it is advantageous for improving the adhesion between the plating base layer and the first metal plating layer. Especially, the carrier is a carbonaceous material, a binder polymer, a polyamide-imide resin, modified polyamide-imide resin, when to these resin is obtained by blending a polysiloxane compound becomes easier to obtain the effect.

  In addition, the amount of catalyst metal used can be reduced as compared with the case where the support surface is almost covered with the catalyst metal. Therefore, it can contribute to resource saving and is advantageous in reducing the cost of the heating member.

  The plating base layer has a portion where the catalyst carrier is exposed on the surface of the first metal plating layer. This means that the catalyst-carrying carrier dispersed in the plating base layer and the catalyst-carrying carrier exposed on the surface can coexist without being exposed on the surface. Therefore, it does not mean that all the catalyst-supporting carriers dispersed in the plating base layer must be exposed.

  The amount of the catalyst-supporting carrier exposed on the surface is not particularly limited, but the catalyst-supporting carrier exposed on the surface is scattered almost uniformly on the surface of the plating base layer. It is preferable. This is because the electroless metal plating can be uniformly deposited starting from the catalyst metal supported on these catalyst-supporting carriers, so that the adhesion between the plating base layer and the first metal plating layer is enhanced. Further, the exposure amount of the catalyst carrier exposed on the surface is not particularly limited as long as there is a portion where the catalyst metal supported on the carrier comes out of the binder polymer.

  In the above plating underlayer, the content of the catalyst-supporting carrier is such that the deposition of electroless metal plating is ensured, the adhesion between the plating underlayer and the first metal plating layer is improved, and the binder polymer. Preferably it is 30 mass parts or more with respect to 100 mass parts, More preferably, it is 50 mass parts or more, More preferably, it can be 100 mass parts or more. On the other hand, the content of the catalyst-supporting carrier is preferably 300 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the binder polymer, from the viewpoints of excellent flexibility of the plating base layer, saturation of the addition effect, economy, and the like. The amount can be 200 parts by mass or less, more preferably 150 parts by mass or less.

  In addition, the thickness of the plating base layer is preferably set to 1 μm or more from the viewpoints of ensuring sufficient adhesion between the base layer and the first metal plating layer, and facilitating the formation of the layer. it can. The thickness of the plating base layer is more preferably 2 μm or more, and further preferably 5 μm or more. On the other hand, the thickness of the plating underlayer is preferably 30 μm or less from the viewpoints of shortening the layer formation time and economy. The thickness of the plating underlayer can be more preferably 20 μm or less, and even more preferably 10 μm or less.

  In the heating member, the first metal plating layer is a layer that can function as a heat generation layer that generates heat by electromagnetic induction heating together with a single metal plating layer or a second metal plating layer described later. Moreover, it is a layer which can be made to function as an electrode at the time of laminating | stacking the 2nd metal plating layer which consists of the electrolytic metal plating mentioned later. The first metal plating layer is laminated on the plating base layer. Specifically, the first metal plating layer can be formed along the outer peripheral surface of the plating base layer. The first metal plating layer is formed by electroless metal plating.

Examples of the metal that forms the first metal plating layer include Cu, Ni, Ag, Pd, Sn, Au, and alloys thereof. Specifically, the metal forming the electroless metal plating layer is, for example, selected from Cu, Ni, Ag, and alloys thereof from the viewpoint of easily ensuring adhesion with the plating base layer. Ru can be a seed or two or more. Ni and Ni alloys are particularly preferable. This is because there are advantages such as excellent catalytic activity with respect to the above-described catalytic metals (particularly Pd) and excellent adhesion to the plating base layer.

  The thickness of the first metal plating layer is preferable from the viewpoints of ensuring adhesion with the plating base layer and facilitating functioning as an electrode when the second metal plating layer described later is formed by electrolytic metal plating. Can be 0.1 μm or more. The thickness of the first metal plating layer is more preferably 0.2 μm or more, and further preferably 0.3 μm or more. On the other hand, the thickness of the first metal plating layer is preferably 2 μm or less from the viewpoint of suppressing cracking during the deformation of the heating member and shortening the layer formation time when the second metal plating layer described later is laminated. be able to. The thickness of the first metal plating layer is more preferably 1 μm or less, and even more preferably 0.5 μm or less. The thickness of the first metal plating layer is preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less when the second metal plating layer described later is not laminated.

The heating member, the first metal plating layer, further, second metal plating layer formed from electroless metal plating or electroless metal plating but it may also be stacked. This second metal plating layer is a layer that can function as a heat generating layer that generates heat mainly by electromagnetic induction heating.

  When it has a 2nd metal plating layer, it becomes easy to select the metal seed | species different from the metal which forms a 1st metal plating layer, or to select thickness different from a 1st metal plating layer. Therefore, the freedom degree of the structure of the metal plating layer in a heating member improves. Therefore, for example, there is an advantage that heat is easily generated by electromagnetic induction heating by selecting a metal having a lower electrical resistance than the first metal plating layer. Further, by forming the second metal plating layer thicker than the first metal plating layer, there is an advantage that heat is easily generated by electromagnetic induction heating. In addition, since it becomes contact | adherence of plating layers between a 1st metal plating layer and a 2nd metal plating layer, favorable adhesiveness is securable. Therefore, if the adhesion between the base layer and the first metal plating layer is ensured, the second metal plating layer hardly peels from the base layer.

  The second metal plating layer is laminated on the first metal plating layer. Specifically, the second metal plating layer can be formed along the outer peripheral surface of the first metal plating layer. The second metal plating layer can be composed of one layer or two or more layers. When the second metal plating layer is composed of a plurality of layers, each layer may be formed from either electrolytic metal plating or electroless metal plating. Each layer may be formed from the same metal or may be formed from different metals. Moreover, the thickness of each layer can also be distributed appropriately.

  Examples of the metal that forms the second metal plating layer include Cu, Ni, Ag, Au, Sn, Zn, and alloys thereof. Specifically, the metal forming the second metal plating layer is selected from Cu, Ni, Ag, and alloys thereof from the viewpoint of good temperature rise by electromagnetic induction heating, for example. It can be a seed or two or more. (Claim 7). Particularly preferred are Cu and Cu alloys. This is because there are advantages such as high temperature rise by electromagnetic induction heating, improved flexibility of the heating member, and excellent economy.

  The thickness of the second metal plating layer is preferably 3 μm or more from the viewpoint of easily ensuring the function as the heat generating layer. The thickness of the second metal plating layer is more preferably 5 μm or more, and even more preferably 10 μm or more. On the other hand, the thickness of the second metal plating layer is preferably 30 μm or less from the viewpoints of flexibility, heat generation in a short time, shortening of the layer formation time, and the like. The thickness of the second metal plating layer is more preferably 20 μm or less, and even more preferably 15 μm or less.

The heating element is on the second metal plating layer, Ru can be further laminated rubber elastic layer. Further, the heating member, the first metal plating layer, Ru can also further laminating a rubber elastic layer. Specifically, the rubber elastic layer can be formed from a rubber composition containing various rubbers. Such a rubber elastic layer is useful because it enables uniform pressurization when the heating member is used in pressure contact with another member.

  Examples of the rubber used for the rubber elastic layer include silicone rubber and fluororubber. These can be used alone or in combination of two or more.

  In addition to rubber, the rubber elastic layer can be added with heat conductive materials such as heat conductive particles, conductive agents, flame retardants, lubricants, plasticizers, softeners, fillers, crosslinking agents, crosslinking aids, anti-aging agents, etc. One or more agents can be included. Examples of the heat conducting material include magnesium oxide, alumina, boron nitride, aluminum nitride, graphite, carbon black, crystalline silica, silicon carbide, and aluminum hydroxide.

  The thickness of the rubber elastic layer is preferably 100 μm or more, more preferably 150 μm or more, and even more preferably 200 μm or more, from the viewpoint of imparting flexibility to the surface of the heating member and improving the ground contact with the object to be heated and other members. can do. On the other hand, the thickness of the rubber elastic layer is preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 300 μm or less, from the viewpoints of improving the IH temperature rising property and thermal conductivity by thinning. .

  The thermal conductivity of the rubber elastic layer can be, for example, 0.3 W / m · K or more. This is because heat loss due to the rubber elastic layer can be reduced and the object to be heated can be efficiently heated. The thermal conductivity of the rubber elastic layer can be preferably 0.5 W / m · K or more. The higher the thermal conductivity of the rubber elastic layer, the better. However, from the viewpoint of flexibility, cost, etc., it can be, for example, 3 W / m · K or less. The thermal conductivity of the rubber elastic layer can be measured with a thermal conductivity measuring device (“HC-110” manufactured by Eihiro Seiki Co., Ltd.) or the like.

  The surface of the rubber elastic layer can be modified by surface treatment. Specifically, F atoms and / or Cl atoms can be introduced into the surface of the rubber elastic layer by surface-treating the surface of the rubber elastic layer with a surface treatment liquid. Further, by applying a light irradiation process such as an ultraviolet irradiation process to the surface of the rubber elastic layer, the surface of the rubber elastic layer can be harder than the inside (reducing the friction coefficient).

  In these cases, the substance attached to the surface of the rubber elastic layer can be easily separated, and release properties can be imparted. Specifically, for example, when used as a fixing member of an image forming apparatus, toner attached to the surface of the rubber elastic layer is easily separated, and toner releasability can be imparted.

  Further, instead of the surface modification of the rubber elastic layer surface as described above, a functional surface layer such as a release layer can be further laminated on the rubber elastic layer. Also in this case, surface functions such as releasability can be imparted. The surface layer can be appropriately selected in consideration of the productivity and cost of the heating member.

  Examples of the main material used for the surface layer include fluorine resins such as polyfluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), and the like for imparting release properties. A rubber etc. can be illustrated. These can be used alone or in combination of two or more. The surface layer may contain one or more additives such as a flame retardant, a filler, a cross-linking agent, a cross-linking aid, a lubricant, a plasticizer, a softener, and an antioxidant.

  The thickness of the surface layer is preferably 5 μm or more, more preferably 10 μm or more from the viewpoint of durability and the like. On the other hand, the thickness of the surface layer is preferably 80 μm or less, more preferably 50 μm or less, from the viewpoint of followability with the lower layer, improvement in thermal conductivity, cost, and the like.

  The application of the heating member is not particularly limited, and can be used to heat various objects to be heated. When the metal plating layer of the heating member is a heat generation layer that generates heat by electromagnetic induction heating, it is excellent in IH temperature rise, so that the object to be heated can be heated quickly when necessary. Therefore, it becomes easy to promote energy saving of the apparatus using the heating member.

Specifically, the heating member can be used as, for example, a fixing member in an electrophotographic image forming apparatus. In this case, the metal plating layer, Ru can be a heat generating layer which generates heat by electromagnetic induction heating. In this case, since the heat generating layer has excellent adhesion and is unlikely to peel off, the heating member is excellent in durability. Therefore, a good image can be formed over a long period of time even when used in a state of being pressed against a pressure roll or the like.

  Examples of the image forming apparatus include a copying machine, a printer, a facsimile machine, a multifunction machine, a POD (Print On Demand) apparatus, etc. that employ an electrophotographic system.

  The heating member manufacturing method includes, for example, a step of applying a layer of a plating base layer forming material containing a binder polymer and a catalyst-supporting carrier to a surface of a base layer formed from the base layer polymer, and the formed coating Removing the binder polymer on the surface of the layer, exposing the catalyst-supporting carrier to form a plating base layer, applying electroless metal plating to the surface of the formed plating base layer, and forming a first metal plating layer; Can have. Furthermore, if necessary, a step of performing electrolytic metal plating or electroless metal plating on the first metal plating layer to form a second metal plating layer can be added.

  According to the manufacturing method of the heating member, the heating member having the above configuration can be obtained. Furthermore, it is not necessary to perform a complicated plating pretreatment process during the production. Therefore, it is possible to contribute to the downsizing of the production line, and the productivity is excellent.

  The manufacturing method of the heating member will be described more specifically. When the base layer is cylindrical, the base layer forming material (paint) is applied to the outer peripheral surface of a cylindrical or columnar mold and dried. If necessary, heat treatment can 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. On the other hand, when the base layer is in the form of a roll, the base layer forming material (kneaded material) is injected into a roll mold and heat-treated. Alternatively, the base layer forming material (kneaded material) can be extruded. Thus, the base layer formed from the base layer polymer is prepared in consideration of the shape of the base layer and the like.

  Then, a plating base layer forming material (paint) containing a binder polymer and a catalyst-carrying carrier is applied to the outer peripheral surface of the base layer and dried. Heat treatment can be performed as necessary. The plating base layer forming material (paint) can be prepared, for example, by dispersing and mixing a binder polymer, a catalyst carrier, and other additives (if necessary) in an appropriate organic solvent. . At this time, the catalyst-supported support is obtained, for example, by applying a catalyst metal precursor (such as an organic compound containing a catalyst metal) to the support surface and then reducing and metallizing the catalyst metal source in the precursor. be able to. Moreover, the method mentioned above is applicable to the coating method. Specifically, a dip coating method can be selected as a coating method from the viewpoint of easy layer formation.

  Next, the binder polymer on the surface of the formed coating layer is removed to expose the catalyst support. Thereby, a plating underlayer can be formed. When the binder polymer can be dissolved by various solvents, the binder polymer can be removed by selectively dissolving (etching) the binder polymer using an appropriate solvent. In addition, it is possible to use removing means such as blasting and polishing.

  After forming the plating base layer, the first metal plating layer can be formed on the plating base layer by performing electroless metal plating using a conventionally known method. Furthermore, a 2nd metal plating layer can be formed by performing electrolytic metal plating on a 1st metal plating layer using a conventionally well-known method as needed. Alternatively, the second metal plating layer can be formed by performing electroless metal plating on the first metal plating layer using a conventionally known method. Furthermore, the manufacturing method of the said heating member can add the process of forming a rubber elastic layer on the 1st metal plating layer surface or the 2nd metal plating layer surface as needed. Moreover, the process of forming a surface layer can also be added to the rubber elastic layer surface as needed.

  In addition, when what has water solubility, such as N-methoxymethylated nylon resin, is used as said binder polymer, when electroless metal plating is performed, it is excellent in the impregnation property of an electroless metal plating solution. . Therefore, removal of the binder polymer can be omitted. In this case, the plating underlayer includes an impregnation layer containing electroless metal plating formed by impregnating an electroless metal plating solution on the first metal plating layer side, in which a catalyst-supporting carrier is dispersed in a binder polymer. Have. Therefore, the electroless metal plating contained in the impregnation layer and the first metal plating layer outside the impregnation layer are combined. In addition, an anchor effect by electroless metal plating in the impregnated layer is also expected. As a result, the adhesion between the base layer and the metal plating layer can be improved.

The heating member according to the embodiment will be specifically described with reference to the drawings.
(Example 1)
As shown in FIGS. 1 to 3, the heating member 1 of Example 1 includes a base layer 2 formed of a base layer polymer, a plating base layer 3 stacked on the base layer 2, and a layer on the plating base layer 3. And a first metal plating layer 4 formed by electroless metal plating. In this example, a second metal plating layer 5 formed by electrolytic metal plating or electroless metal plating is further laminated on the first metal plating layer 4, and on the second metal plating layer 5, Furthermore, the example in which the rubber elastic layer 6 is laminated | stacked is shown.

  In the heating member 1, the base layer 2 is formed in a cylindrical shape. Therefore, in the heating member 1, the plating base layer 3, the first metal plating layer 4, the second metal plating layer 5, and the rubber elastic layer 6 are laminated in this order along the outer peripheral surface of the cylindrical base layer 2.

  In this example, the base layer polymer forming the base layer 2 is specifically a polyamideimide resin. The base layer 2 has a cylinder diameter of about 40 mm, and the base layer 2 has a thickness of about 80 μm. The length of the base layer 2 in the cylinder axis direction is about 350 mm. The thickness of the plating base layer 3 is about 10 μm. Moreover, the 1st metal plating layer 4 is specifically formed by electroless nickel plating, and the thickness is about 0.3 micrometer. The second metal plating layer 5 is specifically formed by electrolytic copper plating or electroless copper plating, and the thickness thereof is about 10 μm. The rubber elastic layer is formed from a silicone rubber composition having thermal conductivity, and the thickness thereof is about 200 μm.

  Here, as shown in detail in FIG. 3, the plating underlayer 3 is formed by dispersing a catalyst-supporting carrier 32 that supports a catalyst metal 322 on the surface of the carrier 321 in a binder polymer 31. The surface of the plating base layer 3 on the first metal plating layer 4 side has a portion where the catalyst carrier 32 is exposed. In this example, the binder polymer 31 is specifically a polyamide-imide resin, and is the same type of resin as the above-described base layer polymer. Further, the carrier 321 in the catalyst carrier 32 is specifically carbon black which is one of carbon-based materials, and the catalyst metal 322 in the catalyst carrier 32 is specifically Pd. The catalyst-supporting carrier 32 includes an exposed portion where the surface of the carrier 321 is exposed and a supporting portion where the catalyst metal 322 is supported.

  Specifically, the heating member 1 of this example is incorporated in an electrophotographic image forming apparatus using a charged image and used as a fixing member (fixing belt). That is, the heating member 1 of this example is for heating the unfixed toner transferred to the paper, which is a heated object.

  Specifically, the heating member 1 of this example is brought into pressure contact with, for example, a pressure roll disposed so as to face the heating member 1 in the fixing unit of the image forming apparatus, and is rotated by following the pressure roll. Can be configured to. In this case, the nip portion can be formed by holding the surface of the heating member 1 and the surface of the pressure roll in pressure contact with each other. Then, a sheet holding an unfixed toner image can be passed through the nip portion, and the unfixed toner image can be melted and fixed on the sheet by heat and pressure from the heating member.

  In addition, the heat_generation | fever of the heating member 1 can be performed as follows, for example. In the fixing unit of the image forming apparatus, an alternating current having a predetermined frequency is applied to the IH coil of the magnetic field generation unit installed with a gap from the outer peripheral surface of the heating member 1. As a result, an alternating magnetic field is generated around the IH coil. When the AC magnetic field crosses the first metal plating layer 4 and the second metal plating layer 5 of the heating member 1, an induced current (eddy current) is generated so as to generate a magnetic field that hinders the change of the AC magnetic field due to electromagnetic induction action. Arise. When the induced current flows through the first metal plating layer 4 and the second metal plating layer 5 of the heating member 1, Joule heat is generated due to electric power proportional to the resistance value of these layers. The two metal plating layer 5 generates heat. Thereby, the heating member 1 can generate heat.

(Example 2)
The heating member 1 of Example 2 is different from the heating member 1 of Example 1 in that the second metal plating layer 5 is not provided as shown in FIG. Therefore, in the heating member 1 of Example 2, the first metal plating layer 4 and the rubber elastic layer 6 are in contact with each other. The rest of the configuration is the same as that of the first embodiment. However, the thickness of the first metal plating layer 4 is about 10 to 15 μm.

  Hereinafter, a plurality of samples of the heating member 1 having different laminated structures were prepared and subjected to various evaluations. An experimental example will be described.

(Experimental example)
<Preparation of various materials>
-Preparation of base layer forming material-
Polyamideimide varnish [HPC-5011-29] manufactured by Hitachi Chemical Co., Ltd. as a base layer polymer was diluted with N-methylpyrrolidone (NMP) so that the solid content concentration was 16% by mass, A base layer forming material was prepared.

-Preparation of catalyst-supported carrier-
As a carrier, 30 g of carbon black [manufactured by Cancarb, “Thermax N990”] as a carbon-based material was prepared. This carbon black was immersed in a 60% by mass nitric acid aqueous solution at 50 ° C. for 10 minutes. Thereby, the carbon black surface was etched. Next, this was filtered and washed with water, and then immersed in an aminocarboxylic acid surfactant (Okuno Pharmaceutical Co., Ltd., “Condizer SP”) at 50 ° C. for 10 minutes. Thereby, the surface adjustment of the carbon black surface was performed. Next, this was filtered and washed with water, and then immersed in a Pd—Sn complex colloidal solution [Okuno Pharmaceutical Co., Ltd., “OPC-80 Catalyst”] at 25 ° C. for 10 minutes. Thereby, the Pd—Sn complex was adsorbed on the carbon black surface. Subsequently, after filtering and washing with water, it was immersed in a 10% by mass hydrochloric acid aqueous solution at 25 ° C. for 10 minutes. This produced metal Pd on the surface of carbon black. Next, this was filtered, washed with water, and dried to obtain powdered Pd-supported carbon.

  6 and 7 show electron scanning micrographs of the obtained Pd-supported carbon. As can be seen from these photographs, it can be seen that the Pd-supported carbon supports Pd particles as a catalyst metal on the surface of carbon black, which is a carrier of the carbon-based material. Moreover, in Pd carrying | support carbon, Pd particle | grains are scattered on the surface of carbon black, and it turns out that the carbon black surface is exposed (exposed). In other words, the exposed portion where the carbon surface as the carrier is exposed and the supporting portion where the Pd particles as the catalyst metal are supported are mixed on the Pd-supported carbon surface.

−Preparation of plating underlayer forming material−
Polyamideimide varnish [HPC-5011-29, manufactured by Hitachi Chemical Co., Ltd.] as a binder polymer and 100 parts by mass of the Pd-supported carbon so that the solid content concentration is 9% by mass. Dispersed and mixed in N-methylpyrrolidone (NMP) as an organic solvent to prepare a plating underlayer forming material.

-Preparation of rubber elastic layer forming material-
A silicone rubber having thermal conductivity [manufactured by Shin-Etsu Chemical Co., Ltd., “X34-2720”] is kneaded with a planetary mixer, and then dissolved in toluene so that the solid content concentration becomes 60% by mass. Thus, a rubber elastic layer forming material was prepared.

-Preparation of electrolytic copper plating solution-
Mixing copper sulfate 70 g / L, sulfuric acid 200 g / L, brightener [Okuno Pharmaceutical Co., Ltd., “Top Lucina LS”] 5 ml / L, 35% hydrochloric acid 0.125 ml / L to prepare an electrolytic copper plating solution did.

<Preparation of heating member of sample 1>
The base layer-forming material was applied to the surface of an aluminum cylindrical mold 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 coating was 100 mm / second. Thereby, a base layer (thickness 80 μm) formed in a cylindrical shape from the polyamideimide resin was produced on the outer peripheral surface of the mold.

  Next, the plating base layer forming material was applied to the surface of the base layer by a dip coating method and dried at 200 ° C. for 30 minutes. The pulling speed at the time of coating was 100 mm / second. As a result, a plating underlayer (thickness: 10 μm) was formed along the outer peripheral surface of the base layer.

  Next, the surface of the plating base layer was etched with a 200 g / L NaOH aqueous solution at 40 ° C. for 10 minutes. As a result, the polyamideimide resin on the surface of the plating base layer was dissolved, and the Pd-supported carbon was exposed on the surface of the plating base layer.

  Next, the base layer on which the plating base layer is formed is immersed in an electroless nickel plating solution [Okuno Pharmaceutical Co., Ltd., “TMP Chemical Nickel HRT”] at 40 ° C. for 5 minutes, and the outer peripheral surface of the plating base layer The 1st metal plating layer (thickness 0.3 micrometer) which consists of electroless nickel plating was formed along these.

Next, electrolytic copper plating is performed on the surface of the first metal plating layer using the electrolytic copper plating solution at a current density of 2.5 A / dm ² and a temperature of 25 ° C. for 20 minutes. A second metal plating layer (thickness 10 μm) made of electrolytic copper plating was formed along the outer peripheral surface.

  Next, the rubber elastic layer forming material was applied to the surface of the second metal plating layer by dip coating, and heat-treated at 130 ° C. for 30 minutes. The pulling speed at the time of coating was 100 mm / second. Thereby, a rubber elastic layer (thickness: 200 μm) was formed along the outer peripheral surface of the second metal plating layer.

  Thus, a heating member of Sample 1 was produced.

<Preparation of heating member of sample 2>
The base layer, the plating underlayer, and the first metal plating layer were formed in the same manner as the preparation of the heating member of Sample 1.

  Next, the base layer formed up to the first metal plating layer is immersed in an electroless copper plating solution [Okuno Pharmaceutical Co., Ltd., “OPC Copper NCA”] at 60 ° C. for 80 minutes, and the first metal plating layer A second metal plating layer (thickness: 10 μm) made of electroless copper plating was formed along the outer peripheral surface of the electrode.

  Thereafter, a rubber elastic layer was laminated on the second metal plating layer in the same manner as in the preparation of the heating member of Sample 1. Thus, a heating member of Sample 2 was produced.

<Preparation of heating member of sample 3>
A base layer was prepared in the same manner as the preparation of the heating member of Sample 1. Next, the surface of the base layer was etched with a 200 g / L NaOH aqueous solution at 40 ° C. for 10 minutes.

  Next, this base layer was immersed in a Pd catalyst-imparting agent [Okuno Pharmaceutical Co., Ltd., “OPC-50 inducer”] at 40 ° C. for 5 minutes. This gave Pd ions to the surface of the base layer. Next, this base layer was immersed in an activator [Okuno Pharmaceutical Co., Ltd., “OPC-150 Cryster”] at 25 ° C. for 5 minutes. This produced metal Pd on the surface of the base layer.

  Thereafter, in the same manner as the preparation of the heating member of Sample 1, a first metal plating layer made of electroless nickel plating, a second metal plating layer made of electrolytic copper plating, and a rubber elastic layer were sequentially laminated on the base layer. . Thus, a heating member of Sample 3 was produced.

<Adhesion evaluation>
In the preparation of each sample, a test piece (size 10 mm × 100 mm) for adhesion evaluation was collected from the sample after forming up to the second metal plating layer. Next, using this test piece, 180 ° peel strength was measured under the condition of a tensile speed of 50 mm / min. This evaluated the adhesiveness between a plating base layer and a metal plating layer.

  As a result, the heating member of Sample 1 had a 180 ° peel strength of 10.5 N / cm. The heating member of Sample 2 had a 180 ° peel strength of 9.8 N / cm. The heating member of Sample 3 had a 180 ° peel strength of 5.2 N / cm.

<Durability evaluation>
A fixing unit mounted on a commercially available full-color multifunction peripheral [manufactured by Konica Minolta, “bizhub C652DS”] was used as a rotating unit, and the heating member for the sample prepared above was attached to the rotating unit. Next, as shown in FIG. 5, the IH coil 11 was placed close to the outer periphery of the sample heating member 1. In FIG. 5, the laminated structure of the heating member 1 is omitted. Next, by rotating the drive motor 21, the pressure roll 12 is rotated through the drive system 22, and the sample heating member 1 pressed against the pressure roll 12 is rotated in the direction of the arrow Y by the rotation. (Rotation speed 300 rpm). Further, the IH coil 11 was operated at 1.25 kW, and the temperature of the rotating sample heating member 1 was increased by electromagnetic induction heating. Then, using a non-contact thermometer 20 [manufactured by Keyence Co., Ltd., “FT-H10”] arranged on the outer periphery of the heating member 1 of the sample, the initial rise until the surface temperature of the sample surface reaches 100 ° C. The warm time was measured.

Next, as shown in FIG. 5, an endurance test was conducted in which 100,000 sheets of A4 printing paper S were passed through the nip N between the heating member 1 of the sample and the pressure roll 12. At this time, the pressure applied by the pressure roll 12 was 4 kgf. After this durability test, the temperature rise time after durability was measured again in the same manner as described above. When the metal plating layer peels or breaks during the durability test, generation of induction current due to electromagnetic induction heating is suppressed, and the temperature rise performance deteriorates. Therefore, when the rate of change in temperature rise performance calculated by the following equation was within 10%, it was determined that the durability was excellent. On the other hand, the time when the rate of change in temperature rise performance exceeded 10% was judged as the life of the heating member of the sample.
Temperature rise performance change rate = (T2-T1 absolute value) / T1 × 100
However, T1: Temperature rise time before the durability test, T2: Temperature rise time after the durability test

  As a result, the heating member of sample 1 and sample 2 had a temperature rise performance change rate within 10% even after passing 100,000 sheets, and there was almost no change. On the other hand, the heating member of Sample 3 had a temperature rise performance change rate of more than 10% after passing about 70,000 sheets.

From the results of the adhesion evaluation and the durability evaluation, the following can be understood.
In other words, the heating member of Sample 3 is a pre-plating treatment, in which electroless nickel plating is deposited using Pd applied to the substrate surface as a nucleus, and the formed first metal plating layer made of electroless nickel plating is used as an electrode. Electrolytic copper plating is applied to form a second metal plating layer. Therefore, the adhesion between the base layer and the first metal plating layer is poor. As a result, when the heating member was used, the metal plating layer was peeled off from the base layer, and the temperature rise due to electromagnetic induction heating was reduced relatively early. That is, it can be said that the heating member of the sample 3 is inferior in durability. Moreover, the heating member of the sample 3 needs to perform a complicated plating pretreatment process before performing various plating treatments on the base layer. Therefore, it can be said that there is a drawback that a huge production line is required.

  On the other hand, it was confirmed that the heating members of Sample 1 and Sample 2 were excellent in adhesion between the base layer and the metal plating layer and had excellent durability. This is due to the following reason.

  In the heating members of Sample 1 and Sample 2, the plating underlayer is formed by dispersing Pd-supporting carbon supporting Pd particles on the surface of carbon black in a binder polymer. Therefore, the base layer polymer and the binder polymer, that is, the polymers are in close contact with each other between the base layer and the plating base layer. Therefore, the adhesion between the base layer and the plating base layer can be improved.

  Further, in the heating members of Sample 1 and Sample 2, the plating underlayer has a portion where the Pd-supporting carbon is exposed on the surface on the first metal plating layer side. When the first metal plating layer is formed, the electroless nickel plating is deposited with the Pd-supporting carbon Pd exposed on the surface of the plating base layer as a nucleus, so that a metal bond is formed between the Pd and the electroless nickel plating. Combined. Moreover, the part which is not exposed to the surface among Pd carrying | support carbon exposed on the surface of the plating base layer is being fixed to the polyamide imide resin which is a binder polymer. Therefore, the adhesion between the plating base layer and the first metal plating layer is improved. Moreover, since it is plating layers between a 1st metal plating layer and a 2nd metal plating layer, it has favorable adhesiveness.

  Therefore, the heating members of Sample 1 and Sample 2 were excellent in adhesion between the base layer and the metal plating layer, and could exhibit excellent durability.

  Further, in this example, a polyamideimide resin in which the base layer polymer and the binder polymer are the same polymer is used. This point is also considered to have worked to improve the adhesion between the base layer and the plating base layer.

  Furthermore, the surface of the Pd-supporting carbon used in this example includes an exposed portion where the carbon surface is exposed and a support portion where Pd particles are supported. The carbon surface has high affinity with the polyamide-imide resin that is a binder polymer. Therefore, it is considered that the Pd-supported carbon is firmly held by the binder polymer, which has been beneficial for improving the adhesion between the plating base layer and the first metal plating layer. Pd and electroless nickel plating can form a good metal bond. This point is also considered to have worked to improve the adhesion between the plating base layer and the first metal plating layer.

  In addition, the adhesion of the metal plating layer can be improved with a small amount of Pd used compared to the case where Pd particles are directly added to the plating base layer. Moreover, it is possible to contribute to cost reduction of the heating member.

  As mentioned above, although the Example of this invention was described in detail, this invention is not limited to the said Example, A various change is possible within the range which does not impair the meaning of this invention. For example, in the above experimental example, the sample according to Example 1 was produced. However, even when the sample is produced according to Example 2, the same effect can be obtained.

DESCRIPTION OF SYMBOLS 1 Heating member 2 Base layer 3 Plating underlayer 31 Binder polymer 32 Catalyst support carrier 321 Support 322 Catalyst metal 4 First metal plating layer 5 Second metal plating layer 6 Rubber elastic layer

Claims (10)

A heating member for heating a heated object,
A base layer made of a polymer for the base layer, a plating base layer laminated on the base layer, and a first metal plating layer laminated on the plating base layer and formed by electroless metal plating; ,
The plating base layer has a portion in which a catalyst-supporting carrier supporting a catalyst metal is dispersed on the surface of the carrier in a binder polymer, and the catalyst-supporting carrier is exposed on the surface of the first metal plating layer. And
The binder polymer, a polyamide-imide resin, modified polyamide-imide resin and one or more der heating member, characterized in Rukoto polysiloxane compound in these resins is selected from those blends. The heating member according to claim 1,
The heating member according to claim 1, wherein the carrier is one or more selected from a carbon-based material, a metal oxide, and silica. The heating member according to claim 1 or 2,
The heating member, wherein the catalyst metal is one or more selected from Pd, Pt, Ag, and alloys thereof. It is a heating member given in any 1 paragraph of Claims 1-3,
The heating member, wherein the metal forming the first metal plating layer is one or more selected from Cu, Ni, Ag, and alloys thereof. It is a heating member given in any 1 paragraph of Claims 1-4,
The heating member, wherein the base layer polymer and the binder polymer contain the same kind of polymer. It is a heating member given in any 1 paragraph of Claims 1-5,
A heating member, wherein a second metal plating layer formed by electrolytic metal plating or electroless metal plating is further laminated on the first metal plating layer. The heating member according to claim 6,
The heating member, wherein the metal forming the second metal plating layer is one or more selected from Cu, Ni, Ag, and alloys thereof. The heating member according to claim 6 or 7,
A heating member, wherein a rubber elastic layer is further laminated on the second metal plating layer. It is a heating member given in any 1 paragraph of Claims 1-5,
A heating member, wherein a rubber elastic layer is further laminated on the first metal plating layer. The heating member according to any one of claims 1 to 9,
A heating member used as a fixing member in an electrophotographic image forming apparatus, wherein the metal plating layer is a heat generating layer that generates heat by electromagnetic induction heating.