JP2016191842A - Heating member and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heating member capable of improving bending durability against repeatedly bending load.SOLUTION: A heating member 1 is for heating a heated member. The heating member 1 has a base layer 2 formed by a polymer for base layer, and a first metal plating layer 4 formed on the base layer 2 by electroless metal plating. The first metal plating layer 4 has a columnar crystal structure 40. The metal plating layer 4 can be formed by executing electroless metal plating with electroless metal plating liquid containing a metal component for forming the first metal plating layer 4 and an amine compound.SELECTED DRAWING: Figure 6

Description

  The present invention relates to a heating member and a manufacturing method thereof.

  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 an electrophotographic copying machine, a printer, or a multi-functional machine generally forms a latent image by exposing image data to a charged photoreceptor, development, transfer to a transfer medium, fixing, and the like. Image formation is performed through the steps. In the fixing process, a heating member having a belt shape or a roll shape is used as the fixing member in order to form an image by melting and fixing the toner transferred to the transfer material (paper) by heating.

  In the field of electrophotographic image forming apparatuses, in recent years, electromagnetic induction heating (hereinafter sometimes abbreviated as IH) heating members have 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 metal layer that generates an induced current by electromagnetic induction heating, and uses the metal layer as a heat generating layer. A metal plating layer is known as the metal layer.

  Prior Patent Document 1 discloses a heating member having a base layer, a plating base layer, and a metal plating layer. This document describes that a metal plating layer is formed on the surface of a plating base layer containing Pd-supporting carbon by using an electroless nickel plating solution (Okuno Pharmaceutical Co., Ltd., “TMP Chemical Nickel HRT”). Yes.

JP2013-210406A

  However, the heating member disclosed in Patent Document 1 has a layered crystal structure of the metal plating layer. Therefore, the toughness with respect to the bending of the metal plating layer is poor. Therefore, in the heating member of Patent Document 1, when a bending load is repeatedly applied, the metal plating layer cannot sufficiently follow the deformation of the base layer, and the metal plating layer peels off. Therefore, the heating member of Patent Document 1 has poor bending durability due to repeated bending loads. Therefore, the heating member of Patent Document 1 still has room for improvement in improving bending durability.

  The present invention has been made in view of the above background, and an object of the present invention is to provide a heating member capable of improving the bending durability due to repeated bending loads.

One aspect of the present invention is a heating member for heating an object to be heated,
A base layer formed from a polymer for the base layer;
A first metal plating layer formed by electroless metal plating on the base layer;
The first metal plating layer is in a heating member having a columnar crystal structure.

Another aspect of the present invention is a method of manufacturing the heating member,
The step of forming the first metal plating layer by performing electroless metal plating using an electroless metal plating solution containing a metal component for forming the first metal plating layer and an amine compound. It is in the manufacturing method of the heating member characterized by having.

  In the heating member, the first metal plating layer has a columnar crystal structure. Therefore, the toughness with respect to the bending of the first metal plating layer is improved. Therefore, when a bending load is repeatedly applied to the heating member, the first metal plating layer can sufficiently follow the deformation of the base layer, and the first metal plating layer is difficult to peel off. Therefore, the heating member can improve the bending durability due to repeated bending loads.

  The manufacturing method of the said heating member performs 1st metal plating by implementing electroless metal plating using the electroless metal plating solution containing the metal component for forming a 1st metal plating layer, and an amine compound. Forming a layer. According to this step, the first metal plating layer having a columnar crystal structure is formed. Therefore, the heating member manufacturing method can preferably manufacture the heating member.

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 the laminated structure typically. It is explanatory drawing which showed typically the microstructure of the 1st metal plating layer. It is explanatory drawing which showed typically the laminated structure in the heating member of Example 2. FIG. It is a scanning electron micrograph of the 1st metal plating layer in the heating member of sample 1 produced in the example of an experiment. It is a scanning electron micrograph of the 1st metal plating layer in the heating member of sample 1C produced in the example of an experiment. It is explanatory drawing which showed typically the outline | summary of the evaluation apparatus used by heat resistance evaluation and IH temperature rising property evaluation in an 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 without being in contact with the heated body.

  The heating member can be used in a state where the surface thereof is pressed against another 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. Further, the other member can be a heated body. 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 bending contact is repeatedly subjected to a bending load. Therefore, in this case, the above-described effects can be sufficiently exhibited.

  In the heating member, the base layer can be formed in a cylindrical shape, for example. In this case, the heating member can have a belt shape and can be suitably 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 exhibit a roll shape and can be suitably used as a heating roll. The base layer can be composed of one layer or two or more layers.

  When the base layer is cylindrical, examples of the base layer polymer used for the base layer include polyamideimide, polyimide, polyethersulfone resin, fluororesin, and polycarbonate resin. These can be used alone or in combination of two or more. These may be modified. These may be blended with a polysiloxane compound or the like.

  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 60 to 100 μm, from the viewpoints of improved durability and ease of manufacture.

  On the other hand, when the base layer is in the form of a roll, the base layer polymer used for the base layer may be a resin or rubber (the rubber also contains an elastomer, hereinafter omitted). As the resin, for example, polyamide imide, polyamide, polyimide, urethane resin, urethane silicone resin, (meth) acrylic resin, (meth) acrylic silicone resin, fluorine resin, or the like can be used. 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 (ECO, CO). ), Isoprene rubber (IR), urethane rubber (U), ethylene-propylene-diene rubber (EPDM), natural rubber (NR), and the like. 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 0.5 to 3 mm, more preferably 1 to 1.5 mm, from the viewpoint of grounding property, cost, and the like.

  The heating member may have a base layer between the base layer and the first metal plating layer. The underlayer can be configured to include a binder polymer and a catalyst. The binder polymer mainly has a role of holding the catalyst in a dispersed state and forming an underlayer.

  In this case, the base layer polymer and the binder polymer, that is, the polymers adhere to each other between the base layer and the base layer. Therefore, in this case, it becomes easy to improve the adhesion of the first metal plating layer to the base layer. Moreover, a 1st metal plating layer can be formed by electroless metal plating, without implementing a complicated plating pretreatment process with respect to a base layer. Therefore, a heating member excellent in manufacturability is obtained.

  As the binder polymer, the various resins and rubbers described above in the description of the base layer polymer can be used.

  In the heating member, the base layer polymer and the binder polymer may be the same type of polymer. In this case, the affinity between the base layer and the base layer is increased, and the adhesion between the base layer and the base layer is easily improved. 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 or the like) are the same type of polymer. Various rubbers classified into a certain type of rubber (silicone rubber, etc.) can be said to be the same polymer. In addition, unmodified polymer and modified polymer, polymers having different molecular weights, polymers having a common polymerization unit, and the like are also included in the concept of the same type of polymer.

  More specifically, both the base layer polymer and the binder polymer can be polyamideimide. In this case, since polyamide imides which are the same kind of polymers are in contact with each other, it becomes easier to further improve the adhesion of the first metal plating layer to the base layer.

  At this time, the ratio of the imide bond to the amide bond of the polyamideimide as the polymer for the base layer and the ratio of the imide bond to the amide bond of the polyamideimide as the binder polymer can both be 1.04 or more. In this case, even when a bending load is repeatedly applied in a heated state, the bending durability can be ensured, which is advantageous in improving the heat resistance of the heating member.

The ratio of the imide bond to the amide bond of the polyamideimide as the polymer for the base layer and the ratio of the imide bond to the amide bond of the polyamideimide as the binder polymer are each preferably 1.05 or more, more preferably 1.06 or more, Preferably it can be 1.08 or more, and even more preferably 1.10 or more. The ratio of the imide bond to the amide bond of the polyamideimide as the polymer for the base layer and the ratio of the imide bond to the amide bond of the polyamideimide as the binder polymer are in view of viscosity controllability during polyamideimide synthesis, toughness of the polyamideimide, etc. Therefore, both can be 1.70 or less, more preferably 1.50 or less, still more preferably 1.35 or less, and even more preferably 1.25 or less. The ratio of the imide bond to the amide bond of the polyamideimide can be calculated by the following (1) based on the composition of the polyamideimide. Polyamideimide includes, for example, aromatic isocyanate compounds such as diphenylmethane diisocyanate (MDI) and tolidine diisocyanate (TODI), trimellitic anhydride (trimellitic anhydride, TMA), 3,3 ′, 4,4 ′. -Biphenyltetracarboxylic dianhydride (BPDA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3' , 4,4'-Diphenylsulfonetetracarboxylic dianhydride (DSDA), pyromellitic anhydride (PMDA) and other aromatic polycarboxylic acid anhydrides, and N-methyl-2-pyrrolidone (NMP) It can form from the compounding material containing nitrogen-containing organic solvent containing N, such as.
(1) Ratio of imide bond to amide bond of polyamideimide = 1 + B × 2 / A
However, A: mol amount (mol) of monomer (TMA etc.) having one carboxylic acid and one acid anhydride
B: Mol amount (mol) of monomer (PMDA, etc.) having two acid anhydrides

  In the heating member, the catalyst of the underlayer is preferably an aggregate of Pd nanoparticles or a Pd-supported carrier that supports Pd on the surface of the carrier. More preferably, the catalyst of the underlayer is an aggregate of Pd nanoparticles from the viewpoint of further improving the adhesion of the first metal plating layer. This is presumably due to the following reasons.

  When the catalyst of the underlayer is an aggregate of Pd nanoparticles, Pd and electroless metal plating are bonded by a metal bond. Further, the electroless metal plating solution penetrates into the aggregate, and the electroless metal plating that forms the first metal plating layer also deposits inside the aggregate of the underlayer. Therefore, in this case, not only the metal bond between Pd and the electroless metal plating, but also the electroless metal plating deposited inside the aggregate serves as an anchor, and between the base layer and the first metal plating layer. The anchor effect is thought to increase. As a result, it is considered that the adhesion of the first metal plating layer can be further improved. In this case, since electroless metal plating is deposited as described above, the plating reactivity tends to be good. The aggregate of Pd nanoparticles may contain a hydrophilic dispersant. This is because the electroless metal plating solution easily penetrates into the aggregates, and the above-described effects can be easily obtained.

  On the other hand, when the catalyst of the underlayer is a Pd-supported carrier, Pd and electroless metal plating are bonded by metal bonding. The carrier is fixed to the binder. Therefore, in this case, not only the metal bond between Pd and electroless metal plating, but also the support fixed to the binder serves as an anchor, and the catalyst is not as much as when the catalyst is an aggregate of Pd nanoparticles. An anchor effect occurs between the formation and the first metal plating layer. Therefore, in this case, it is easy to improve the adhesion of the first metal plating layer.

  For the above reasons, when the catalyst of the underlayer is an aggregate of Pd nanoparticles, it is advantageous for improving the adhesion of the first metal plating layer as compared with the case where the catalyst of the underlayer is a Pd carrier. In addition, when the catalyst of the underlayer is an aggregate of Pd nanoparticles, the plating reactivity of the first metal plating layer is improved compared to the case where the catalyst of the underlayer is a Pd-supported carrier, and the underlayer It becomes easy to deposit a 1st metal plating layer on the whole surface of. Therefore, when the catalyst of the underlayer is an aggregate of Pd nanoparticles, it is advantageous for forming a uniform first metal plating layer.

  In the aggregate of Pd nanoparticles, the Pd nanoparticles are nano-sized particles. The particle size (primary particle size) of the Pd nanoparticles is preferably 1 nm to 40 nm, more preferably 2 nm to 30 nm, and even more preferably 3 nm to 20 nm, from the viewpoint of plating reactivity, paint dispersibility, and the like. . The particle size (secondary particle size) of the aggregate is preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and still more preferably 30 nm to 100 nm, from the viewpoint of plating reactivity, paint dispersibility, and the like. it can. Each of the above particle diameters is an average value obtained from a transmission electron microscope image.

  In addition, the carrier in the Pd-supporting carrier can have various particle shapes such as a spherical shape, a substantially spherical shape, a fibrous shape, a columnar shape, a lump shape, and a substantially tufted shape. Moreover, as a material of a support | carrier, it can be made into 1 type, or 2 or more types selected from a carbonaceous material, a metal oxide, and a silica, for example. 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 easy loading of Pd, affinity with the binder polymer, economy, and the like.

  The average particle diameter of the carrier is preferably 0.01 to 10 μm, more preferably 0.05 to 0.05 from the viewpoints of good dispersibility in the binder polymer and easy to ensure the smoothness of the underlayer surface. It can be 5 μm, more preferably 0.1 to 2 μm. The particle size of the carrier is the particle size (diameter) d50 when the volume-based cumulative frequency distribution measured by the laser diffraction / scattering method shows 50%. As a laser diffraction / scattering type particle diameter / particle size distribution measuring apparatus, “Microtrac UPA-EX150” manufactured by Nikkiso Co., Ltd. is used.

  In the heating member, the catalyst is preferably exposed on the surface of the underlayer. When the catalyst is an aggregate of Pd nanoparticles, specifically, a part of the aggregate may be exposed on the surface of the underlayer. Further, when the catalyst is a Pd-supported carrier, the carrier portion supporting Pd may be exposed on the surface of the underlayer.

  In the above heating member, when the catalyst is an aggregate of Pd nanoparticles, the thickness of the underlayer is determined by the formability of the underlayer, ensuring adhesion between the base layer and the first metal plating layer, and the aggregate on the surface of the underlayer. From the viewpoint of easy exposure, reduction of material cost, etc., it is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.3 μm to 2 μm. On the other hand, when the catalyst is a Pd-supported carrier, the thickness of the underlayer is preferably from the viewpoints of formability of the underlayer, ensuring adhesion between the base layer and the first metal plating layer, reducing the material cost, and the like. It can be 3 μm to 30 μm, more preferably 0.5 μm to 10 μm, and even more preferably 1 μm to 5 μm.

  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 base layer. Specifically, the first metal plating layer can be formed along the outer peripheral surface of the base layer.

  Specifically, the metal forming the first metal plating layer may be made of Ni or a Ni alloy. In this case, the catalytic activity for Pd is high, which is advantageous for improving the adhesion with the underlayer. In addition, Ni or Ni alloy is a hard metal compared with metals, such as Cu. However, in the heating member, the first metal plating layer has a columnar crystal structure. Therefore, even when the first metal plating layer is made of Ni or a Ni alloy, the toughness against bending of the first metal plating layer can be improved. For this reason, the above-described effects can be sufficiently exhibited. Ni or Ni alloy can contain one or more elements such as P and B.

  The thickness of the first metal plating layer is preferably from the viewpoint of ensuring adhesion with the base layer and easily functioning as an electrode when forming the second metal plating layer described later by electrolytic metal plating. It 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 said heating member can be set as the structure which has the 2nd metal plating layer formed by electrolytic metal plating or electroless metal plating on the 1st metal plating layer. The second metal plating layer is a layer that can function as a heat generation layer that generates heat mainly by electromagnetic induction heating. The second metal plating layer can be composed of one layer or two or more layers.

  In this case, it becomes easy to select a metal type different from the metal forming the first metal plating layer or to select a thickness different from that of the first metal plating layer. Therefore, the freedom degree of the structure of the metal plating layer in a heating member improves. Therefore, for example, by selecting a metal having a lower electrical resistance than that of the first metal plating layer, there is an advantage that the heating member can easily generate heat by electromagnetic induction heating. Further, by forming the second metal plating layer thicker than the first metal plating layer, there is an advantage that the heating member can easily generate heat 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.

  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. . 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, more preferably 5 μm or more, still more preferably 10 μm or more, even more preferably 15 μm or more, and even more, from the viewpoint of facilitating ensuring the function as the heat generating layer. More preferably, it can be more than 15 μm. On the other hand, the thickness of the second metal plating layer is preferably 30 μm or less, more preferably 28 μm or less, and even more preferably 25 μm or less, from the viewpoints of flexibility, heat generation in a short time, and shortening of the layer formation time. Can do.

  The heating member may have a rubber elastic layer on the second metal plating layer. In addition, the heating member may have a rubber elastic layer on the first metal plating layer. In this case, uniform pressure can be applied when the heating member is used in pressure contact with another member. In addition, you may interpose a primer layer between each metal plating layer and a rubber elastic layer as needed.

  Specifically, the rubber elastic layer can be formed from a rubber composition containing various rubbers. 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 conductive 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 viewpoint of improving the IH temperature rise 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.).

  The said heating member can be set as the structure which has a surface layer on a 2nd metal plating layer.

  In this case, since the powder such as toner attached to the surface of the heating member is easily separated, it can be suitably used as a fixing member of the image forming apparatus.

  The main material used for the surface layer is, for example, polyfluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), etc., from the viewpoint of improving the releasability of powder such as toner. Fluorine-based resin, fluororubber, and the like can be exemplified. 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 viewpoints of followability to layers below the surface layer, improved thermal conductivity, cost, and the like.

  In the heating member, the surface of the rubber elastic layer may be surface-modified by surface treatment without forming a surface layer. 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). Also in this case, since the powder such as toner attached to the surface of the heating member is easily separated, it can be suitably used as a fixing member of the image forming apparatus.

  The heating member can be used to heat various objects to be heated. When the first metal plating layer, or the first metal layer and the second metal plating layer of the heating member are heat generation layers that generate heat by electromagnetic induction heating, the IH temperature rise performance is excellent. A to-be-heated body can be heated rapidly. 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, a fixing member having improved bending durability due to repeated bending loads can be obtained.

  Examples of the electrophotographic image forming apparatus include an electrophotographic copying machine using a charged image, a printer, a facsimile machine, a multifunction machine, an on-demand printing machine, and the like.

  The manufacturing method of the said heating member performs 1st metal plating by implementing electroless metal plating using the electroless metal plating solution containing the metal component for forming a 1st metal plating layer, and an amine compound. Forming a layer.

  The amine compound functions as a complexing agent. Examples of the amine compound include glycine, alanine, ethylenediamine, propanediamine, and the like. These can be used alone or in combination of two or more. The electroless metal plating solution can be prepared, for example, by adding an amine compound to a known electroless metal plating solution. The content of the amine compound in the electroless metal plating solution can be, for example, about 1 to 50 g / L.

  More specifically, the method for manufacturing the heating member can be performed as follows, for example. A base layer is formed from the base layer polymer. An underlayer is formed on the base layer from an underlayer forming material containing a binder and a catalyst. The underlayer forming material may be applied in layers on the base layer by, for example, various coating methods such as brush coating, dip coating, roll coating, and spray coating. Further, depending on the material of the binder polymer, the base layer can be formed by heat-treating the base layer forming material applied on the base layer. Further, if necessary, the surface of the base layer can be etched or polished to remove a part of the binder on the surface of the base layer to expose the catalyst. The catalyst can be easily exposed by coating the base layer forming material on the base material in the nanometer order. In this case, etching and polishing can be omitted. Electroless metal plating is performed on the surface of the underlayer with an electroless metal plating solution having the components described above to form a first metal plating layer. Thereafter, if necessary, electrolytic metal plating is performed on the first metal plating layer with an electrolytic metal plating solution to form a second metal plating layer. Moreover, a rubber elastic layer is formed on the second metal plating layer as necessary. Further, a surface layer is formed on the rubber elastic layer as necessary. As described above, the heating member can be preferably manufactured. Moreover, in the manufacturing method of the said heating member, after a base layer is abbreviate | omitted, Pd catalyst is provided to the base layer surface, after Pd was made to exist, the electroless metal plating which has the component mentioned above on the base layer surface which has Pd on the surface It is also possible to form an electroless metal plating with a liquid to form a first metal plating layer.

  In addition, each structure mentioned above can be arbitrarily combined as needed, in order to acquire each effect etc. which were mentioned above.

  The heating member and its manufacturing method according to the embodiment will be specifically described with reference to the drawings.

Example 1
As shown in FIGS. 1 to 4, the heating member 1 of this example includes a base layer 2 formed from a base layer polymer, and a first metal plating layer 4 formed on the base layer 2 by electroless metal plating. Have. The first metal plating layer 4 has a columnar crystal structure 40. The details will be described below.

  In this example, the heating member 1 has a base layer 3 between the base layer 2 and the first metal plating layer 4. The heating member 1 has a second metal plating layer 5 formed by electrolytic metal plating or electroless metal plating on the first metal plating layer 4. The heating member 1 has a rubber elastic layer 6 on the second metal plating layer 5. The heating member 1 has a surface layer 7 on the rubber elastic layer 6.

  In this example, the base layer 2 is formed in a cylindrical shape. Therefore, the heating member 1 has a belt shape, and along the outer peripheral surface of the cylindrical base layer 2, the base layer 3, the first metal plating layer 4, the second metal plating layer 5, the rubber elastic layer 6, and The surface layer 7 is laminated in this order. Specifically, the base layer polymer that forms the base layer 2 is polyamideimide. The ratio of the imide bond to the amide bond of the polyamideimide is 1.04 or more. The cylinder diameter of the base layer 2 is about 40 mm, the thickness of the base layer 2 is about 80 μm, and the length of the base layer 2 in the cylinder axis direction is about 350 mm.

  In this example, the underlayer 3 includes a binder polymer 31 and a catalyst 32 as shown in FIG. 2 and 4, the catalyst 32 is omitted. The binder polymer 31 is specifically polyamideimide. The ratio of the imide bond to the amide bond of the polyamideimide is 1.04 or more. The catalyst 31 is an aggregate 322 of Pd nanoparticles 321. Aggregates 322 of Pd nanoparticles 321 include Pd nanoparticles 321 not only on the surface but also inside. The underlayer 3 includes an aggregate 322 of Pd nanoparticles 321 exposed on the surface of the underlayer 3. In addition to the aggregates 322 of the Pd nanoparticles 321 exposed on the surface of the foundation layer 3, the foundation layer 3 may include aggregates 322 of the Pd nanoparticles 321 that are not exposed on the surface of the foundation layer 3. The underlayer 3 may have non-aggregated Pd nanoparticles 321 in addition to the aggregates 322 of Pd nanoparticles 321. Note that the Pd component in the aggregate 322 of Pd nanoparticles 321 acts as a nucleus of plating growth when the first metal plating layer 3 is formed by electroless metal plating. The thickness of the underlayer 3 can be about 0.3 μm to 2 μm.

  In this example, the metal forming the first metal plating layer 3 is specifically Ni or a Ni alloy. As schematically shown in FIG. 4, the first metal plating layer 4 has a columnar crystal structure 40. The columnar crystal structure 40 is formed by plating growing in a direction perpendicular to the surface of the base layer 2. The first metal plating layer 3 is formed by performing electroless metal plating using an electroless metal plating solution containing a metal component for forming the first metal plating layer 3 and an amine compound. . The thickness of the 1st metal plating layer 3 can be about 0.1-2 micrometers. In FIG. 4, the catalyst 32 of the underlayer 3 is omitted. In FIG. 3, the columnar crystal structure 40 is omitted.

  In this example, the second metal plating layer 5 is formed by electrolytic metal plating. Specifically, the metal forming the second metal plating layer 5 is Cu or Cu alloy, or Ag or Ag alloy. The thickness of the second metal plating layer can be about 15 to 30 μm.

  In this example, the rubber elastic layer 6 is formed from a rubber composition having thermal conductivity. The rubber used for the rubber elastic layer 6 is specifically silicone rubber or fluororubber. The thickness of the rubber elastic layer 6 can be about 100 to 300 μm.

  In this example, the surface layer 7 is made of a fluororesin. The thickness of the surface layer 7 can be about 5 to 80 μm.

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

  Specifically, the heating member 1 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 being driven by the pressure roll. Can be configured. 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 the heat and pressure of the heating member 1.

  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)
As shown in FIG. 5, the heating member 1 of Example 2 has the second metal plating layer 5 in that the catalyst of the underlayer 3 is a Pd-supported carrier 320 that supports Pd321 on the surface of the carrier 323. This is different from the heating member 1 of Example 1 in that there is no surface layer 7. 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. Other configurations are the same as those of the first embodiment. However, the thickness of the underlayer is about 1 μm to 5 μm. Moreover, the thickness of the 1st metal plating layer 4 shall be about 0.1-30 micrometers.

  Hereinafter, a plurality of samples of heating members having different configurations were prepared and evaluated. An experimental example will be described.

(Experimental example)
<Preparation of various materials>
-Preparation of polyamideimide varnish-
Into a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a cooling tube, the respective materials were charged according to the blending ratios in Table 1 so that N-methyl-2-pyrrolidone (NMP) had a solid content of 26%. The mixture was charged and heated to 160 ° C. over 1 hour with stirring under a nitrogen stream. The reaction was continued at 160 ° C. for about 10 hours, and then the reaction was stopped. This prepared polyamideimide varnish (PAI varnish) AG (solid content concentration: 26 mass%).

-Base layer forming material-
Polyamideimide varnish A is the base layer forming material (1), Polyamideimide varnish B is the base layer forming material (2), Polyamideimide varnish C is the base layer forming material (3), and Polyamideimide varnish D is the base layer forming material (4) ), Polyamideimide varnish E as base layer forming material (5), polyamideimide varnish F as base layer forming material (6), and polyamideimide varnish G as base layer forming material (7). The base layer polymer in the base layer forming materials (1) to (7) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.22 in the base layer forming material (1). Forming material (2) is 1.67, Base layer forming material (3) is 1.11, Base layer forming material (4) is 1.04, Base layer forming material (5) is 1.11, Base layer forming material The material (6) is 1.67 and the base layer forming material (7) is 1.00.

-Underlayer forming material-

  Polyamideimide varnish A and a Pd nanoparticle aggregate (primary particle size 5 nm, secondary particle size 50 nm) used in Iox's “Metaloid”, with a paint viscosity of about 100 mPa · s (25 ° C.) An undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (1). The binder polymer in the base layer forming material (1) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.22.

  Polyamideimide varnish B and Pd nanoparticle aggregates (primary particle size 5 nm, secondary particle size 50 nm) used in “Metaloid” manufactured by Iox Co., Ltd., with a paint viscosity of about 100 mPa · s (25 ° C.) An undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (2). The binder polymer in the base layer forming material (2) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.67.

  Polyamideimide varnish C and a Pd nanoparticle aggregate (primary particle size 5 nm, secondary particle size 50 nm) used in Iox's “Metaloid”, with a paint viscosity of about 100 mPa · s (25 ° C.) An undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (3). The binder polymer in the material for forming the underlayer (3) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.11.

  Polyamideimide varnish D and Pd nanoparticle aggregates (primary particle size 5 nm, secondary particle size 50 nm) used in “Metaloid” manufactured by Iox Co., Ltd., with a paint viscosity of about 100 mPa · s (25 ° C.) An undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (4). The binder polymer in the base layer forming material (4) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.04.

  Polyamideimide varnish E and aggregates of Pd nanoparticles (primary particle size 5 nm, secondary particle size 50 nm) used in “Metaloid” manufactured by IOX, with a paint viscosity of about 100 mPa · s (25 ° C.) The undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (5). The binder polymer in the base layer forming material (5) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.11.

  Polyamideimide varnish F and aggregates of Pd nanoparticles (primary particle size 5 nm, secondary particle size 50 nm) used in “Metaloid” manufactured by IOX, with a paint viscosity of about 100 mPa · s (25 ° C.) The undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (6). In addition, the binder polymer in the base layer forming material (6) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.67.

  Polyamideimide varnish G and Pd nanoparticle agglomerates (primary particle size 5 nm, secondary particle size 50 nm) used in Iox's “Metaloid”, with a paint viscosity of about 100 mPa · s (25 ° C.) An undiluted coating solution (manufactured by Iox) was used as the underlayer-forming material (7). The binder polymer in the base layer forming material (7) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.00.

  By dispersing and mixing polyamideimide varnish A: 100 parts by mass and Pd-supported carbon: 120 parts by mass in N-methyl-2-pyrrolidone (NMP) so that the solid content concentration is 7.5% by mass. A base layer forming material (8) was prepared. The binder polymer in the base layer forming material (8) is polyamideimide, and the ratio of the imide bond to the amide bond of the polyamideimide is 1.22.

  In the preparation of the base layer forming material (8), the Pd-supported carbon was prepared as follows. As a carrier, 30 g of carbon black (“Thermax N990” manufactured by Cancarb Co., Ltd.), which is 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 colloid 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. Subsequently, Pd carrying carbon was obtained by filtering, washing with water, and drying.

-Degreasing solution-
A degreasing solution was prepared by mixing 200 ml of an alkaline degreasing agent (Okuno Pharmaceutical Co., Ltd., “OPC-190 Cleaner”), 1200 ml of 3% by weight caustic soda, and 600 ml of ion-exchanged water.

-Electroless metal plating solution for forming the first metal plating layer-
Nickel sulfate hexahydrate: 26 g / L, sodium hypophosphite monohydrate (reducing agent): 32 g / L, glycine (complexing agent): 7.5 g / L, sodium citrate dihydrate ( Complexing agent): An electroless metal plating solution (1) was prepared by mixing 30 g / L.

  By mixing nickel sulfate hexahydrate: 26 g / L, sodium hypophosphite monohydrate (reducing agent): 32 g / L, sodium citrate dihydrate (complexing agent): 30 g / L An electroless metal plating solution (2) was obtained. The electroless metal plating solution (2) does not contain glycine, which is a kind of amine compound.

-Electrolytic metal plating solution for forming second metal plating layer-
Electrolytic metal plating by 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 A liquid was prepared.

-Rubber elastic layer forming material-
By kneading a silicone rubber having thermal conductivity (“X34-2133” manufactured by Shin-Etsu Chemical Co., Ltd.) with a planetary mixer, and then dissolving in toluene so that the solid content concentration becomes 60% by mass, A rubber elastic layer forming material was prepared.

-Surface layer forming material-
A tube (thickness 30 μm) made of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA) was prepared as a material for forming the surface layer.

<Heating member for Sample 1 to Sample 6 and Sample 9>
A predetermined base layer forming material shown in Table 1 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 coating was 100 mm / second. Thereby, a cylindrical base layer (thickness 80 μm) made of polyamideimide (PAI) was formed on the outer peripheral surface of the cylindrical pipe.

  Next, a predetermined base layer forming material shown in Table 1 was applied to the surface of the base layer by a brush coating method, heat-treated at 120 ° C. for 15 minutes, and further heat-treated at 240 ° C. for 15 minutes. Thereby, a base layer (0.5 μm) was formed on the outer peripheral surface of the base layer. Thereafter, the base layer on which the underlayer was formed was immersed in a degreasing solution at 65 ° C. for 5 minutes, and then rinsed with pure water. Thereby, the surface of the underlayer was degreased. The underlayer contains polyamideimide (PAI) as a binder polymer and Pd nanoparticle aggregates as a catalyst. Further, the surface of the underlayer was etched with a degreasing solution, and as a result, a part of the Pd nanoparticle aggregates was exposed on the surface of the underlayer.

  Next, the base layer on which the underlayer was formed was immersed in an electroless metal plating solution (1) (plating solution temperature: 84 ° C., plating time: 5 minutes), and then rinsed with pure water. Thereby, the 1st metal plating layer (thickness 1 micrometer) was formed on the outer peripheral surface of a base layer. The first metal plating layer is formed by electroless Ni plating. Further, as a result of observing the cross section of the first metal plating layer with a scanning electron microscope, a large number of columnar crystals grown in a direction perpendicular to the surface of the base layer were observed as representatively shown in FIG. From this result, it was confirmed that the first metal plating layer has a columnar crystal structure 40.

Next, electrolytic metal plating was performed on the surface of the first metal plating layer using an electrolytic metal plating solution at a current density of 2.5 A / dm ² and a temperature of 25 ° C. for 20 minutes. Thereby, the 2nd metal plating layer (thickness 20 micrometers) was formed on the outer peripheral surface of a 1st metal plating layer. The second metal plating layer is formed by electrolytic Cu plating.

  Next, a 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 during coating was 100 mm / sec. Thereby, a rubber elastic layer (thickness: 200 μm) made of silicone rubber was formed on the outer peripheral surface of the second metal plating layer.

  Subsequently, the surface of the rubber elastic layer was covered with a tube-shaped surface layer forming material. Thus, a fluororesin surface layer (thickness 30 μm) was formed on the outer peripheral surface of the rubber elastic layer.

  Thus, the heating members of Sample 1 to Sample 6 and Sample 9 were produced.

<Heating member of sample 7>
A base layer was formed 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. Subsequently, this base layer was immersed in an activator (Okuno Pharmaceutical Co., Ltd., “OPC-150 Cryster”) at 25 ° C. for 5 minutes. As a result, metal Pd was generated on the surface of the base layer instead of the underlayer.

  Thereafter, the first metal plating layer, the second metal plating layer, the rubber elastic layer, and the surface layer were formed in this order on the base layer in the same manner as the preparation of the heating member of Sample 1. Thus, a heating member of sample 7 was produced. The first metal plating layer in the heating member of sample 7 had a columnar crystal structure.

<Heating member of sample 8>
A base layer was formed in the same manner as the preparation of the heating member of Sample 1. Next, using the base layer forming material (8) containing Pd-supporting carbon instead of the Pd nanoparticle aggregates, the base layer forming material (8) is applied to the surface of the base layer by a brush coating method. After heat treatment at 15 ° C. for 15 minutes, heat treatment was further performed at 240 ° C. for 15 minutes. Thereby, a base layer (thickness 1.5 μm) was formed on the outer peripheral surface of the base layer.

  Thereafter, the base layer is formed on the base layer in the same manner as in the preparation of the heating member of Sample 1, except that the plating conditions of the first metal plating layer are the plating solution temperature: 90 ° C. and the plating time: 6 minutes. The 1st metal plating layer, the 2nd metal plating layer, the rubber elastic layer, and the surface layer were formed in this order. Thus, a heating member of Sample 8 was produced. In addition, the 1st metal plating layer in the heating member of the sample 8 had a columnar crystal structure.

<Heating member of sample 1C>
Sample 1C was prepared in the same manner except that the electroless metal plating solution (2) containing no amine compound was used instead of the electroless metal plating solution (1) containing an amine compound in the preparation of the heating member of sample 1. A heating member was prepared. As a result of observing the cross section of the first metal plating layer with a scanning electron microscope, as shown in FIG. 7, the first metal plating layer had plating grown in a direction parallel to the base layer surface. From this result, it was confirmed that the first metal plating layer has a layered crystal structure 40C.

<Bending durability>
A strip-shaped test piece (15 mm × 115 mm) was cut out from the sample heating member so that the belt circumferential direction and the longitudinal direction coincided with each other, and the MIT folding fatigue tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 25 ° C. × 50% RH MIT test was performed using “MIT-DA”), and the number of MIT was measured. The test conditions were a load of 1 kg with a spring interposed, a repetition rate of 175 cycles / minute, a deflection angle of 45 °, and a tip R (curvature radius when bent) of 0.38 mm. The number of MITs serves as an index for evaluating bending durability, and the greater the number of MITs, the better the bending durability. At this time, the case where the number of MIT times is 5000 times or more is “A” as being excellent in bending durability due to repeated bending loads, and the case where the number of MIT times is 2000 times or more and less than 5000 times is that bending durability due to repeated bending loads is good “B”, and “C” as the case where the number of MIT was 2000 times or less was inferior in bending durability due to repeated bending load.

<Plating adhesion>
A strip-shaped test piece having a length of 10 cm and a width of 1 cm was taken from the heating member of the sample. In order not to cut the test piece, an incision was made at the interface between the base layer (sample 7 is the base layer) and the first metal plating layer using a cutter knife. Then, using a tensile tester (manufactured by Shimadzu Corporation, “Precision Universal Testing Machine AGS-1kNX”), the upper layer above the first metal plating layer is pulled, and the base layer (sample 7 is the base layer) and the first metal plating layer Adhesion strength between them (180 ° peel strength) was measured. At this time, the tensile speed was 25 mm / min.

  “A +” when the adhesion strength is 5 N / cm or more, “A” when the adhesion strength is 3 N / cm or more and less than 5 N / cm, and “A−” when the adhesion strength is 1 N / cm or more and less than 3 N / cm. The case where the adhesion strength was less than 1 N / cm was defined as “C”.

<Heat resistance>
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 a sample heating member was attached to the rotating unit. Next, as shown in FIG. 8, the IH coil 91 was placed close to the outer periphery of the sample heating member 1. In FIG. 8, the laminated structure of the heating member 1 is omitted. Next, by rotating the drive motor 92, the pressure roll 94 is rotated through the drive system 93, and the sample heating member 1 that is in pressure contact with the pressure roll 94 is rotated in the direction indicated by the arrow Y. (Rotation speed 300 rpm). In FIG. 8, N is a nip portion between the sample heating member 1 and the pressure roll 94. S is printing paper. Further, the IH coil 91 was operated at 1.25 kW, and the temperature of the rotating sample heating member 1 was increased by electromagnetic induction heating. Then, the sample heating member 1 was continuously heated for 1 hour in a state where the surface temperature at the central portion in the cylinder axis direction reached 230 ° C. The surface temperature was measured using a non-contact thermometer 95 (manufactured by Keyence Corporation, “FT-H10”) disposed on the outer periphery of the heating member 1 of the sample. Then, the sample heating member 1 was rotated for 1 hour while maintaining the temperature of 230 ° C. Then, the MIT test mentioned above was done and the number of MIT was measured. The deterioration rate (%) of the number of MITs was calculated by an equation of 100 × (initial number of MITs−number of MITs after heating) / (initial number of MITs). “A” when the deterioration rate of the MIT frequency is 5% or less, “B” when the deterioration rate of the MIT frequency is more than 5% and 10% or less, and “C” when the deterioration rate of the MIT frequency is more than 10%. did.

<Plating reactivity>
A base layer having Pd on the surface (Sample 7 is a base layer having Pd on the surface) was prepared in accordance with the manufacturing conditions of the sample heating member. Then, using a predetermined electroless metal plating solution, the relationship between the plating solution temperature and the plating deposition state by visual inspection was investigated. The case where the first metal plating layer was deposited on the whole at a plating solution temperature of 80 ° C. was designated as “A +”, and the case where the first metal plating layer was deposited on the whole at a plating solution temperature of 90 ° C. was designated as “A”.

<IH temperature rise>
As explained in the above “heat resistance”, the IH coil 95 was operated at 1.25 kW, and the temperature of the heating member 1 of the rotating sample was raised by electromagnetic induction heating. And the temperature rising time until the surface temperature of a sample reaches 200 degreeC was measured using the said non-contact thermometer 95 arrange | positioned on the outer periphery of the heating member 1 of a sample. The case where the temperature rise time was 20 seconds or less was “A”, the case where the temperature rise time was more than 20 seconds to less than 30 seconds was “B”, and the case where the temperature rise time was 30 seconds or more was “C”. In addition, this test investigated the basic performance at the time of using the heating member 1 as a fixing member.

  Table 1 shows the composition of the polyamide-imide varnish, and Table 2 shows the detailed configuration, manufacturing conditions, evaluation results, and the like of the sample heating member.

According to Table 1, Table 2, FIG. 6, and FIG.
The heating member of Sample 1C has a first metal plating layer formed using an electroless metal plating solution (2) that does not contain an amine compound. Therefore, the crystal structure of the first metal plating layer is not columnar but layered. Therefore, the first metal plating layer in the heating member of Sample 1C has poor toughness against bending. Therefore, when a bending load is repeatedly applied to the heating member of sample 1C, the first metal plating layer having a layered crystal structure cannot sufficiently follow the deformation of the base layer, and the first metal plating layer Peeled off. As a result, the heating member of Sample 1C was inferior in bending durability due to repeated bending loads.

  On the other hand, the heating members of Sample 1 to Sample 9 have a first metal plating layer formed using an electroless metal plating solution (1) containing an amine compound. Therefore, the crystal structure of each first metal plating layer in each heating member is not a layered shape but a columnar shape. Therefore, the toughness with respect to the bending of the 1st metal plating layer in each heating member improved. Therefore, when a bending load is repeatedly applied to each heating member, each first metal plating layer having a columnar crystal structure can sufficiently follow the deformation of each base layer, and each first metal plating layer It was difficult to peel off. Therefore, each heating member was able to improve the bending durability due to repeated bending loads.

  Further, when the heating members of Sample 1 to Sample 9 are compared, the following can be understood. When a base layer containing a binder polymer and a catalyst is provided between the base layer and the first metal plating layer, the base layer polymer and the binder polymer are in close contact with each other between the base layer and the base layer. Become. Therefore, in this case, it is easy to improve the adhesion of the first metal plating layer to the base layer. Further, in this case, the first metal plating layer can be formed by electroless metal plating without performing a complicated plating pretreatment process on the base layer, and it is easy to obtain a heating member excellent in productivity. It can be said. At this time, when both the base layer polymer and the binder polymer are polyamideimides, the polyamideimides of the same kind are in contact with each other, so that the adhesion of the first metal plating layer to the base layer can be further improved. In particular, when the ratio of the imide bond to the amide bond of the polyamideimide as the polymer for the base layer and the ratio of the imide bond to the amide bond of the polyamideimide as the binder polymer are both 1.04 or more, the heated state Even when a bending load is repeatedly applied, it can be said that it is advantageous in improving the heat resistance of the heating member because the bending durability can be ensured.

  Further, it can be seen that when the catalyst of the underlayer is an aggregate of Pd nanoparticles, it is advantageous for improving the adhesion of the first metal plating layer as compared with the case where the catalyst of the underlayer is Pd-supported carbon. This is presumably due to the following reasons. When the catalyst of the underlayer is an aggregate of Pd nanoparticles, Pd and electroless metal plating are bonded by a metal bond. Further, the electroless metal plating solution penetrates into the aggregate, and the electroless metal plating that forms the first metal plating layer also deposits inside the aggregate of the underlayer. Therefore, in this case, not only the metal bond between Pd and the electroless metal plating, but also the electroless metal plating deposited inside the aggregate serves as an anchor, and between the base layer and the first metal plating layer. The anchor effect is thought to increase. As a result, it is considered that the adhesion of the first metal plating layer can be further improved. Further, when the catalyst of the underlayer is an aggregate of Pd nanoparticles, the plating reactivity of the first metal plating layer is improved as compared with the case where the catalyst of the underlayer is Pd-supported carbon, and the surface of the underlayer is improved. It becomes easy to deposit a 1st metal plating layer on the whole. Therefore, when the catalyst of the underlayer is an aggregate of Pd nanoparticles, it can be said that it is advantageous for forming a uniform first metal plating layer.

  Even if the above-described configuration is adopted, the IH temperature rise performance can be sufficiently ensured. Therefore, it can be said that the heating members of Sample 1 to Sample 9 are suitable as a fixing member (here, a fixing belt) in an electrophotographic image forming apparatus.

  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.

DESCRIPTION OF SYMBOLS 1 Heating member 2 Base layer 3 Underlayer 4 First metal plating layer 40 Columnar crystal structure 5 Second metal plating layer 6 Rubber elastic layer 7 Surface layer

Claims (10)

A heating member for heating a heated object,
A base layer formed from a polymer for the base layer;
A first metal plating layer formed by electroless metal plating on the base layer;
The heating member, wherein the first metal plating layer has a columnar crystal structure. An underlayer is provided between the base layer and the first metal plating layer;
The heating member according to claim 1, wherein the underlayer includes a binder polymer and a catalyst.   The heating member according to claim 1 or 2, wherein the catalyst is an aggregate of Pd nanoparticles or a Pd-supported carrier that supports Pd on the surface of the carrier.   The heating member according to claim 2, wherein the base layer polymer and the binder polymer are both polyamideimides.   The ratio of the imide bond to the amide bond of the polyamideimide as the polymer for the base layer and the ratio of the imide bond to the amide bond of the polyamideimide as the binder polymer are both 1.04 or more. The heating member according to 1.   The heating member according to any one of claims 1 to 5, wherein the metal forming the first metal plating layer is Ni or a Ni alloy.   The heating according to any one of claims 1 to 6, further comprising a second metal plating layer formed by electrolytic metal plating or electroless metal plating on the first metal plating layer. Element.   The heating member according to claim 7, further comprising a rubber elastic layer on the second metal plating layer.   The heating member according to claim 1, wherein the heating member is used as a fixing member in an electrophotographic image forming apparatus. It is a manufacturing method of the heating member according to claim 1,
The step of forming the first metal plating layer by performing electroless metal plating using an electroless metal plating solution containing a metal component for forming the first metal plating layer and an amine compound. A method for manufacturing a heating member, comprising: