JP2015189053A - Resin-coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve adhesiveness between a substrate and a coating layer while keeping favorable properties (for example, slidability and mold releasability) of a fluorine resin and to suppress damage to the substrate when a resin layer is worn or scratched, in a resin-coated article having the resin layer containing the fluorine resin on the substrate.SOLUTION: A resin-coated article includes a substrate having irregularities, in which at least a surface layer having the irregularities is metallic, and a resin layer that coats the irregularities of the substrate. The main component of the surface layer is copper, a copper alloy, lead, a lead alloy, aluminum, or an aluminum alloy. The resin layer contains a perfluoro-polymer, at least a part of which is cross-linked or graft-modified. Preferably, the resin layer further contains an engineering plastic. Preferably, the perfluoro-polymer and at least a part of the engineering plastic are cross-linked or graft-modified.

Description

  The present invention relates to a resin coating.

  The fluororesin is excellent in slidability, releasability, heat resistance, chemical resistance, weather resistance, and the like. Therefore, fluororesins are used as coating materials for various products. As a product coated with fluororesin (fluorine resin coating), for example, an inner pot such as a rice cooker or a home bakery, a household product such as an electric pan, a hot plate or a frying pan, or a sliding member such as a bearing (for example, JP 2007-016243), resin mold releasing jigs such as extrusion die heads and die of extrusion molds (for example, Japanese Patent Laid-Open Nos. 05-220812 and 2012-025079), a toner fixing roller of a laser printer and so on.

  On the other hand, fluororesins generally tend to have poor wear resistance and adhesion. Accordingly, it has been proposed to improve the wear resistance and adhesion of the fluororesin by irradiating the fluororesin with ionizing radiation to cause a crosslinking reaction (for example, JP2013-027875A and JP2011). No. -074938, Japanese Patent No. 3702801).

JP 2007-016243 A Japanese Patent Laid-Open No. 05-220812 JP 2012-025079 A JP 2013-027875 A JP 2011-074938 A Japanese Patent No. 3702801

  A fluororesin crosslinked by irradiation with ionizing radiation has improved wear resistance compared to an uncrosslinked fluororesin. However, in a fluororesin coating such as a sliding member in which a resin layer containing a fluororesin is formed on a substrate, the resistance against damage of the fluororesin coating layer due to point sliding or scratching is not necessarily sufficient, and the substrate and the fluororesin The adhesiveness with the coating layer is not dramatically improved under the conditions of point sliding and scratching, and there is still room for improvement.

  The present invention has been made on the basis of the above circumstances, and in a resin coating in which a resin layer containing a fluororesin is formed on a substrate, advantageous characteristics of the fluororesin (for example, slidability, mold release, etc.) It is intended to improve the adhesion between the substrate and the coating layer while suppressing the damage to the substrate when the resin layer is worn away or scratched by scratching. .

  The present invention comprises a substrate having irregularities, and at least the surface layer including the irregularities is made of metal, and a resin layer coated on the irregularities of the substrate. The main component of the surface layer is copper, copper alloy, lead , Lead alloy, aluminum or aluminum alloy, wherein the resin layer contains a perfluoropolymer, and at least a part of the perfluoropolymer is crosslinked or graft-modified.

  According to the present invention, in a resin coating in which a resin layer containing a fluororesin is formed on a substrate, resistance to abrasion and scratching is enjoyed while enjoying the advantageous properties (for example, slidability and releasability) possessed by the fluororesin. And adhesiveness can be improved.

It is typical sectional drawing which shows the principal part of the resin coating which concerns on the 1st Embodiment of this invention. It is typical sectional drawing which shows the state which the resin coating material of FIG. 1 worn out. FIG. 2 is a schematic plan view showing a state where the resin coating of FIG. 1 is worn. It is typical sectional drawing for demonstrating the manufacturing method of the resin coating of FIG. It is typical sectional drawing for demonstrating the manufacturing method of the resin coating of FIG. It is a typical perspective view which shows the bending bearing which is an example of the resin coating of FIG. FIG. 4B is a schematic cross-sectional view taken along line X1-X1 in FIG. 4A. It is a typical perspective view which shows the protrusion bearing which is the other example of the resin coating material of FIG. It is typical sectional drawing which follows the X2-X2 line | wire of FIG. 5A. It is typical sectional drawing which shows the metal mold | die for extrusion molding for demonstrating the resin moldability jig | tool which is another example of the resin coating material of FIG. It is typical sectional drawing which shows the metal mold | die for extrusion molding for demonstrating the resin moldability jig | tool which is another example of the resin coating material of FIG. It is typical sectional drawing which shows the principal part of the resin coating which concerns on the 2nd Embodiment of this invention. It is typical sectional drawing which shows the principal part of the resin coating which concerns on the 3rd Embodiment of this invention.

[Description of Embodiment of the Present Invention]
The present invention made to solve the above-mentioned problems comprises a substrate having irregularities, and at least a surface layer including the irregularities is made of metal, and a resin layer coated on the irregularities of the substrate, The component is copper, copper alloy, lead, lead alloy, aluminum or aluminum alloy, and the resin layer contains a perfluoropolymer, and at least a part of the perfluoropolymer is crosslinked or graft-modified. It is.

  Since the resin layer of the resin coating includes a perfluoropolymer that is at least partially crosslinked or graft-modified, the resin layer is excellent in slidability and releasability, and a conventional non-crosslinked fluororesin is used. The wear resistance is improved as compared with the resin coating. In addition, since the surface layer of the substrate has irregularities, it becomes a barrier that reduces damage to the surface layer of the substrate when abrasion of the resin layer progresses or scratches are caused by scratching, and the progress of damage is stopped. . In addition, even in such a case, the specific metal has a low sliding resistance and hardly loses its original characteristics, and the substrate of the resin coating has irregularities. For this reason, the surface (sliding surface) of the resin coating has a structure in which the convex portions of the base are exposed and the base and the fluororesin are mottled when the resin layer is worn away. Covers the metallic substrate, so that substantial substrate exposure can be suppressed. As a result, the resin coating can easily maintain the advantageous properties (for example, slidability and releasability) of the fluororesin, and in addition to the unevenness of the surface layer of the substrate, it can protect and reduce sliding resistance. In addition, a slidability reproduction effect and the like can be obtained. In addition, the anchor effect improves wear resistance, scratch resistance, and adhesion between the substrate and the resin layer. Therefore, the resin coating is excellent in slidability and releasability, and has improved wear resistance and adhesion between the substrate and the resin layer.

  In the resin coating, when the resin layer is worn more than a certain thickness, the substrate is exposed. At this time, since the surface layer of the substrate of the resin coating has irregularities, the convex portions of the surface layer are exposed. By using the metal having high slidability as a main component as the surface layer, the metal portion having high slidability is exposed when the convex portion is exposed. Thereby, in the said resin coating, even if a resin layer is worn out more than fixed thickness and a base | substrate (metal layer) is exposed, the outstanding slidability can be maintained. As a result, the resin coating has excellent wear durability and can achieve a long service life.

  The resin layer may further include an engineering plastic. Thus, the characteristic of a resin layer can be improved because a resin layer contains an engineering plastic. For example, by including PEEK (polyetheretherketone) resin as an engineering plastic in the resin layer, the properties (for example, abrasion resistance and mechanical strength) of the PEEK resin can be imparted to the resin layer.

  It is preferable that at least a part of the engineering plastic and the perfluoropolymer are crosslinked or graft-modified. By such crosslinking, the mechanical strength of the resin layer is further improved and the wear resistance is further improved.

  The crosslinking or graft modification is preferably performed by irradiation with ionizing radiation at least at a temperature equal to or higher than the melting point of the perfluoropolymer. As described above, the irradiation of the ionizing radiation at a temperature equal to or higher than the melting point can appropriately promote the crosslinking of the perfluoropolymer. As a result, the mechanical strength of the resin layer is more appropriately improved and the wear resistance is more appropriately improved.

  The ionizing radiation may be irradiated at a temperature equal to or higher than the melting point of the engineering plastic. When the resin layer contains an engineering plastic, the irradiation of ionizing radiation at a temperature equal to or higher than the melting point as described above appropriately promotes the crosslinking or graft modification of the perfluoropolymer and also partially bridges the engineering plastic. Graft modification can also be promoted, and further crosslinking or graft modification between the perfluoropolymer and the engineering plastic can be promoted. As a result, the mechanical strength of the resin layer is more appropriately improved and the wear resistance is more appropriately improved.

  The arithmetic average roughness (Ra) of the surface of the surface layer may be 1 μm or more and 1,000 μm or less, but preferably 5 μm or more and 200 μm or less. Thus, by setting the arithmetic average roughness of the surface of the surface layer within the above range, resistance to abrasion and scratching and adhesion of the resin layer to the substrate can be improved more appropriately.

  The substrate may have a substrate body on which the surface layer is laminated. The base body is preferably made of metal, resin or ceramic. As described above, since the substrate has the surface layer and the substrate body, various roles can be given to the substrate body by selecting the material of the substrate body. For example, by forming the base body from a metal having high thermal conductivity such as aluminum, Joule heat generated by friction on the surface of the resin layer can be effectively released from the base body. In this case, it can suppress that the said resin coating becomes high temperature at the time of use of the said resin coating, and can suppress that the said resin coating is thermally deteriorated.

  Here, the “main component” is a component having the highest content, for example, a component having a content of 50% by mass or more. “Arithmetic average roughness (Ra)” is a value measured according to JIS-B-0601: 2001. The “mixed resin coating” includes at least a bearing, a cylinder for an actuator, a piston member, a sliding member such as a component member of a gear pump sliding surface, and a resin releasable jig. The “resin releasable jig” refers to a jig having a contact portion with a molten resin and having a high releasability with respect to the resin of the contact portion. Specifically, the “resin releasable jig” is an extrusion die (extrusion die) used for extruding an extruded product, such as an apparatus that extrudes, conveys and forms at least a molten resin such as a resin molding die. Dies, extrusion points, T dies, extrusion die caps, etc.).

[Details of the embodiment of the present invention]
Hereinafter, the resin coating of the present invention, a bearing which is an example of the resin coating, and a resin releasable jig will be described with reference to the drawings.

[First Embodiment]
<Resin coating>
The resin coating 1 in FIG. 1 includes a base 10 and a resin layer 11. The shape of the resin coating 1 is not particularly limited, and examples thereof include a flat plate, a curved plate, a block, a bent product, and a drawn product. An example of the bent product is a bending bearing 3 described later with reference to FIGS. 4A and 4B, and an example of the drawn product is an extruded bearing 4 described later with reference to FIGS. 5A and 5B. Examples of the blocks include resin releasable jigs 5 and 5A which will be described later with reference to FIGS.

<Substrate>
The base 10 has a base body 12 and a metal layer 13.

(Base body)
The base body 12 is made of, for example, metal, plastic such as polyimide, ceramic, glass, or the like. The base body 12 is preferably made of metal. Examples of the metal include Al, Al alloy, iron, iron alloy (including SUS), Ni, Ni alloy, Ti, Ti alloy, Cu, Cu alloy (including brass), and cemented carbide.

(Metal layer)
The metal layer 13 contributes to improving the adhesiveness of the resin layer 11 and extending the life of the resin coating 1. The metal layer 13 corresponds to the surface layer and is laminated on the base body 12. The metal layer 13 has a plurality of convex portions 14, and the surface layer includes irregularities by these convex portions 14.

  The arithmetic average roughness (Ra) (degree of unevenness) of the surface of the metal layer 13 can be 1 μm or more and 1,000 μm or less, preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less. If the arithmetic average roughness (Ra) is less than the lower limit, the wear resistance, scratch resistance, and adhesion between the metal layer 13 (substrate 10) and the resin layer 11 may not be sufficiently increased. On the other hand, when the arithmetic average roughness (Ra) exceeds the upper limit, it is difficult to suppress damage to the base 10 when the resin layer 11 is worn away and scratched. In addition, it may be difficult to sufficiently increase the adhesion between the metal layer 13 (base 10) and the resin layer 11.

  Examples of the method for forming irregularities include chemical etching, electrochemical etching, embossing, blasting, and the like. Moreover, the said unevenness | corrugation may be formed simultaneously with the formation of the metal layer 13 by forming the metal layer 13 by thermal spraying or plating.

  As the material of the metal layer 13, copper, copper alloy, lead, lead alloy, aluminum, or aluminum alloy is used. These metals are preferable because they have high adhesion and slidability with the base body 12. Among these, as a material of the metal layer 13, copper and a copper alloy are preferable from an environmental side.

<Resin layer>
The resin layer 11 ensures the slidability, releasability, etc. of the resin coating 1. The resin layer 11 covers the unevenness of the metal layer 13. The resin layer 11 preferably contains a perfluoropolymer. In some cases, the resin layer 11 is preferably transparent.

  Here, “transparent” refers to a case where the average transmittance for light in the range of 350 nm to 800 nm when the resin layer 11 is formed with an average thickness of 2 mm is 60% or more.

  The resin layer 11 may contain an engineering plastic as a suitable component in addition to the perfluoropolymer, and may contain other optional components as long as the effects of the present invention are not impaired.

(Perfluoropolymer)
The perfluoropolymer is at least partially crosslinked or graft modified. Examples of the crosslinking or graft modification method include known methods, but ionizing radiation irradiation is preferred. Details of ionizing radiation irradiation will be described later.

  Here, the perfluoropolymer is a polymer that does not contain hydrogen atoms composed of carbon atoms and fluorine atoms, or an atom other than carbon atoms and fluorine atoms (for example, oxygen atoms) in a polymer chain composed of carbon atoms and fluorine atoms. It means a polymer containing a perfluoro group having an atom) (for example, a perfluoropolyether group or the like).

  Specific examples of the perfluoropolymer include polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene / hexafluoropropylene copolymer (FEP). It is done. These perfluoropolymers may be used alone or in combination of two or more, or may be used after being modified. A commercially available product can be used as the perfluoropolymer. In this case, a single species may be used alone, or a plurality of species may be used in combination.

(Engineering plastic)
The engineering plastic is for improving the characteristics of the resin layer 11. At least a part of this engineering plastic is preferably crosslinked or graft-modified alone, and is preferably crosslinked or graft-modified with the perfluoropolymer. By such crosslinking or graft modification, the mechanical strength of the resin layer 11 is further improved, and the wear resistance is further improved.

  As said engineering plastic, it can select and use from a well-known thing according to the characteristic provided to the resin layer 11, and can typically use PEEK resin.

  This PEEK resin is a thermoplastic resin having a structure in which a benzene ring is bonded to the para position and the benzene rings are connected by a rigid carbonyl group (—C═O) or a flexible ether bond (—O—). . The PEEK resin is excellent in wear resistance, heat resistance, insulation, workability, and the like. When the PEEK resin is included in the resin layer 11, the wear resistance, adhesion, and the like of the resin layer 11 are improved. .

  A commercial item can be used as PEEK resin. As PEEK resins, those of various grades are commercially available, and a single grade of PEEK resin that is commercially available may be used alone, or multiple grades of PEEK resin may be used in combination. Modified PPEK resin may be used.

  Although there is no limitation in particular as content of engineering plastics, 20:80 or more and 80:20 or less are preferable and 35:65 or more and 65:35 or less are more preferable by mass ratio with a perfluoropolymer. If the content of the engineering plastic is less than the above lower limit, the characteristics (for example, wear resistance) of the resin layer 11 may not be sufficiently improved. On the other hand, if the content of the engineering plastic exceeds the above upper limit, the advantageous properties (for example, slidability and releasability) of the perfluoropolymer may not be sufficiently developed.

  As the engineering plastic, polyamideimide (PAI) or a modified product thereof (hereinafter also referred to as “PAI resin”) can be used. The resin layer 11 includes a PAI resin, so that the adhesion with the metal layer 13 is improved. In addition, although the PAI resin is not as wear-resistant as PEEK, it has higher hardness than the perfluoropolymer, so that the hardness of the resin layer 11 can be increased.

(Optional component)
Examples of the optional component include an adhesive component, a crosslinking aid, and a flame retardant.

  As the adhesive component, a resin having higher adhesiveness to the substrate 10 (metal layer 13) is preferable to the perfluoropolymer. Examples of such an adhesive component include the above-described PAI resin, polyether sulfone, and the like.

  As content of the adhesive component in the resin layer 11, it is 5 mass% or more and 40 mass% or less with respect to the total resin part, Preferably it is 10 mass% or more and 30 mass% or less. When the content of the adhesive component in the resin layer 11 is in the above range, it is easy to effectively maintain the characteristics of the perfluoropolymer as the base material component.

<Advantages>
Since the resin layer 11 of the resin coating 1 includes a perfluoropolymer that is at least partially crosslinked or graft-modified, the resin layer 11 is excellent in slidability and releasability and is made of an uncrosslinked fluororesin. Abrasion resistance is improved compared to the conventional resin coating used. Further, since the metal layer (surface layer) 13 of the base body 10 has irregularities, the damage to the metal layer 13 (surface layer) of the base body 10 is reduced when the resin layer 11 is worn or scratched by scratching. It becomes a barrier to prevent the progress of damage. In addition, even in such a case, the specific metal has a small sliding resistance and hardly loses its original characteristics, and the substrate 10 of the resin coating 1 has irregularities. Therefore, the surface (sliding surface) of the resin coating 1 has a mottled structure when the unevenness of the substrate 10 is exposed as the abrasion of the resin layer 11 progresses. 13 (surface layer) can be covered, and substantial exposure of the substrate 10 can be suppressed. As a result, the resin coating 1 is easy to maintain the advantageous properties (for example, slidability and releasability) possessed by the fluororesin such as perfluoropolymer. In addition, the resin coating 1 is protected by the unevenness of the surface layer of the substrate 10. An effect, a sliding resistance reduction effect, a sliding property reproduction effect, etc. can be acquired. In addition, wear resistance, scratch resistance, and adhesion between the substrate 10 and the resin layer 11 are improved by the anchor effect. Therefore, the resin coating 1 has improved wear resistance and adhesion between the substrate 10 and the resin layer 11 in addition to slidability and releasability.

  Further, as shown in FIGS. 2A and 2B, when the resin layer 11 is worn by a certain thickness or more due to the wear of the resin layer 11, the metal layer (surface layer) 13 has irregularities, so The part 14 is exposed. On the other hand, when the metal layer 13 is formed of a metal having high slidability, the exposed convex portion 14 also has high slidability. Therefore, in the resin coating 1, the resin layer 11 has a constant thickness. Even if the substrate 10 (metal layer 13) is exposed due to wear as described above, excellent slidability can be maintained. As a result, the resin coating 1 has excellent wear durability, and a long life can be realized.

  Depending on usage, if the resin layer 11 is transparent, the unevenness of the metal layer (surface layer) 13 is visually recognized through the resin layer 11. On the other hand, when the resin layer 11 is worn and the base 10 is exposed, the convex portion 14 of the metal layer (surface layer) 13 is exposed as described above. Here, when the unevenness can be visually recognized through the resin layer 11 in a state where the substrate 10 is not exposed, the exposed protrusion 14 and the resin layer 11 are removed when the protrusion 14 of the metal layer (surface layer) 13 is exposed due to wear. It is difficult to distinguish from the unevenness that is visually recognized. As a result, even if the base body 10 is exposed due to wear of the resin layer 11, it is possible to suppress the appearance of the resin coating 1 from deteriorating.

<Method for producing resin coating>
An example of a method for producing the resin coating 1 will be described with reference to FIGS. 3A and 3B.

  First, as shown in FIG. 3A, a laminate 2 of a base material layer 20 and a metal layer 21 is formed.

  As the base material layer 20, for example, a material made of metal, plastic such as polyimide, ceramic, glass or the like is used.

  The metal layer 21 is made of metal such as copper, copper alloy, lead, lead alloy, aluminum, aluminum alloy, for example. Examples of the method for forming the metal layer 21 include known film forming methods such as vapor deposition, sputtering, CVD, plating, and thermal spraying.

  The laminate 2 may be formed as a clad when the base material layer 20 is formed of a metal. This clad can be formed by, for example, two types of metal plates, metal foil or the like by rolling or ultrasonic bonding. When the laminate 2 is formed of two kinds of metals such as clad, the base layer 20 is formed of a metal having high thermal conductivity (heat dissipation) such as aluminum, and the metal layer 21 is slid of copper or the like. It is preferable to form the metal with high property. When the resin coating 1 of FIG. 1 is formed from such a laminate 2, heat dissipation is ensured by the base body 12 having high heat dissipation, and the resin layer 11 is more than a predetermined thickness by the metal layer 13 having high slidability. Even if the metal layer 13 (convex portion 14) is exposed due to wear (as shown in FIGS. 2A and 2B), the slidability can be appropriately ensured.

  Next, as shown in FIG. 3B, irregularities are formed on the surface of the metal layer 21. As for the unevenness, the arithmetic average roughness (Ra) (degree of unevenness) of the surface of the metal layer 21 can be 1 μm or more and 1,000 μm or less, preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less. preferable.

  As a method for forming the unevenness, a known roughening treatment can be applied. Examples of the roughening treatment include chemical etching, electrochemical etching, embossing, and blasting. Of these, chemical etching and electrochemical etching are preferable.

  Examples of chemical etching include known methods such as alkali etching and acid etching. The alkali etching is performed by bringing an alkali solution such as a sodium hydroxide solution into contact with the surface of the metal layer 21. The acid etching is performed by bringing an acid solution such as a mixed solution of phosphoric acid and sulfuric acid into contact with the surface of the metal layer 21.

The electrochemical etching is performed, for example, by applying alternating current, pulse current, or half-wave rectification to the laminate 2 in a state where the laminate 2 is immersed in an aqueous solution containing chlorine ions. As said aqueous solution, the thing whose chlorine ion concentration is 0.1 mass% or more and pH is 0.01-3.0 is preferable, for example. The current density of the applied current, 0.1~1.0A / cm ² is preferred.

  In electrochemical etching, selection of a chemical solution, its concentration, a printing current, and the like vary greatly depending on the type of metal, and therefore it is preferable to select them as appropriate within a range that can be adjusted by those skilled in the art.

  Moreover, when the target unevenness | corrugation (roughness) is obtained when the metal layer 21 is formed in the base material layer 20, the formation process of an unevenness | corrugation may be abbreviate | omitted. For example, when the metal layer 21 is formed by thermal spraying, plating, sputtering, or the like, it is possible to obtain irregularities with arithmetic average roughness (Ra) in the above range by selecting film forming conditions.

  Next, the resin coating 1 shown in FIG. 1 can be obtained by forming the resin layer 11 so as to cover the unevenness of the metal layer 21.

  The resin layer 11 is formed by, for example, irradiating a coating film obtained by coating and drying a resin composition with ionizing radiation.

(Resin composition)
Examples of the resin composition include those obtained by dispersing resin particles and, if necessary, additives in a dispersion medium.

  Resin particles include resin particles mainly composed of perfluoropolymer as an essential component, and if necessary, resin particles mainly composed of engineering plastics such as PEEK resin as suitable components. Other resin particles whose main component is a resin other than the above may be included. The resin particles may be solid particles or may exist as an emulsion dispersoid.

  As said resin particle, 20 mass% is preferable, as for content of the resin particle whose particle size is less than 1 micrometer, 50 mass% is more preferable, and 80 mass% or more is further more preferable. On the other hand, the upper limit of the content of the resin particles is preferably 100% by mass. For example, a resin particle or resin particle lump having a large particle diameter of about several μm to several tens of μm is likely to fall off during friction, and thus durability (life) may be reduced. On the other hand, by using a resin composition in which the content of particles having a particle size of less than 1 μm is not less than the lower limit, a frictional force acts on the resin layer 11 formed from the resin composition by sliding or the like. Detachment of the resin particles is suppressed.

  When the resin particles include resin particles containing engineering plastic as a main component in addition to resin particles containing perfluoropolymer as a main component, the weight ratio of these resin particles is 20:80 or more and 80: 20 is preferable, and 35:65 or more and 65:35 is more preferable. A specific mass ratio may be determined according to characteristics required for a coating film formed from the mixed resin composition. That is, the mass ratio may be determined depending on how much the characteristics of the perfluoropolymer and the characteristics according to the type of engineering plastic such as PEEK resin are developed. For example, when emphasizing characteristics such as releasability and slidability, the mass of the perfluoropolymer may be made larger than the mass of the PEEK resin so that the characteristics of the perfluoropolymer are expressed predominately. On the other hand, when emphasizing the mechanical strength (abrasion resistance) and the adhesion between the coating film and the material to be coated such as the coating film, PEEK resin is used as an engineering plastic, and the mass of the PEEK resin is changed to perfluorocarbon. What is necessary is just to make it increase rather than the mass of a polymer and to express the characteristic of PEEK resin predominantly.

  Additives include organic or inorganic fillers, plasticizers, stabilizers, and the like. As the filler, colorant, plasticizer and stabilizer, known ones can be used as long as the effects of the present invention are not impaired.

  Examples of the dispersion medium include water, an organic solvent, a mixed solvent thereof, and the like. Among these, water is preferable.

(Coating of resin composition)
The resin composition can be applied by a known method. The coating method is not particularly limited, and examples thereof include a dipping method, a spin coating method, a gravure coating method, a roll coating method, a spray coating method, and the like, and are appropriately selected depending on the shape of the coating object.

(Drying resin composition)
The drying of the resin composition may be either natural drying or forced drying as long as the dispersion medium can be evaporated, and forced drying is preferable from the viewpoint of shortening the drying time. Moreover, when heating a coating film at the time of ionizing radiation irradiation with respect to a coating film, you may make it evaporate a dispersion medium as preheating before ionizing radiation irradiation.

(Ionizing radiation irradiation to coating film)
The ionizing radiation irradiation is performed to crosslink or graft-modify at least a part of the coating film. When at least a part of the perfluoropolymer in the coating is crosslinked or graft-modified by irradiation of ionizing radiation to the coating and contains an engineering plastic such as PEEK resin, at least a part of the engineering plastic It can be crosslinked or graft modified with a perfluoropolymer and crosslinked or graft modified.

  Examples of the ionizing radiation include charged particle beams such as electron beams and high-energy ion beams, high-energy electromagnetic waves such as γ-rays and X-rays, and neutral beams. Among these, electron beams are preferable. This is because the electron beam generator is relatively inexpensive, a high-power electron beam can be obtained, and the degree of crosslinking can be easily controlled.

  The irradiation dose of the ionizing radiation may be arbitrarily used since an effect is obtained in a wide range, but is preferably about 50 KGy to 800 KGy. If the irradiation dose of ionizing radiation is less than the above lower limit, crosslinking may be insufficient and sufficient wear resistance, adhesion, and the like may not be obtained. On the other hand, when the irradiation dose of ionizing radiation exceeds the above upper limit, decomposition of the resin component (breakage of the polymer main chain) becomes excessive, and the wear resistance may be reduced. On the other hand, if the irradiation dose is 50 to 800 kGy, the crosslinking of the resin proceeds sufficiently and the decomposition of the resin component is small, so that sufficient wear resistance, adhesion, and the like can be obtained. Therefore, by setting the irradiation dose within the above range, the mixed resin molded body has properties such as slidability, releasability, wear resistance, and adhesiveness more appropriately.

  The ionizing radiation irradiation is preferably performed in a state where the coating film is heated in a low-oxygen or oxygen-free atmosphere.

  By performing ionizing radiation irradiation in a low-oxygen or oxygen-free atmosphere, the adhesive force of the resin layer 11 to the metal layer 13 can be improved. Specifically, if the oxygen concentration is less than 1000 ppm, an effect of improving the adhesive force can be obtained. When the oxygen concentration is 500 ppm or less, a remarkable effect of improving the adhesive force is obtained, and when the oxygen concentration is 100 ppm or less, a more remarkable effect of improving the adhesive force is obtained. From the viewpoint of stability and ease of control of the oxygen concentration during ionizing radiation irradiation, the oxygen concentration is preferably 10 ppm or less.

  The heating temperature of the coating film during irradiation with ionizing radiation is preferably equal to or higher than the melting point of the perfluoropolymer. When the engineering resin such as PEEK resin is included in the resin composition, the heating temperature is preferably equal to or higher than the melting points of the perfluoropolymer and engineering plastic. The heating temperature is preferably 80 ° C. or higher than the melting point, more preferably 40 ° C. or lower than the melting point. For example, when the perfluoropolymer is PTFE and the PEEK resin as an engineering plastic is mixed, the melting point of PTFE is 327 ° C. and the melting point of the PEEK resin is 334 ° C. Therefore, the heating temperature is 344 ° C. to 367 ° C. preferable. By performing the heating temperature at a temperature higher than the melting point of the resin, crosslinking of the resin can be appropriately promoted. On the other hand, by setting the upper limit of the heating temperature to 80 ° C or higher than the melting point of the resin, the thermal decomposition of the resin (breaking of the polymer main chain) can be suppressed, and the deterioration of slidability and wear resistance can be suppressed. it can.

<Bearing>
Next, a bearing which is a typical example of the resin coating 1 will be described with reference to FIGS. 4A and 4B or FIGS. 5A and 5B. 4A and 4B show a wound bearing, and FIGS. 5A and 5B show a protruding bearing. In addition, below, the duplication description with the matter demonstrated in the said resin coating 1 may be abbreviate | omitted.

(Winding bearing)
4A and 4B is formed in a substantially cylindrical shape as a whole. The dimension of the winding bearing 3 is appropriately determined according to the application. In one example, the winding bearing 3 has dimensions of an outer diameter of 1 cm to 3 cm, an inner diameter of 0.5 cm to 2.9 cm, a height of 0.5 cm to 3 cm, and a thickness of 1 mm to 5 mm.

  The winding bearing 3 includes a substantially cylindrical base 30 and a resin layer 31 formed on the inner surface of the base 30.

  The base body 30 includes a base body 32 and a metal layer 33. The base body 32 and the metal layer 33 correspond to the base body 10 and the metal layer 13 of the resin coating 1 in FIG. 1, respectively.

  The resin layer 31 is for ensuring the slidability of the sliding surface (inner surface) in the bending bearing 3. This resin layer 31 corresponds to the resin layer 11 of the resin coating 1 in FIG.

  Such a bending bearing 3 is obtained, for example, by forming a laminated body of the base body 32, the metal layer 33, and the resin layer 31 into a strip-shaped flat plate, and bending the laminated body into a cylindrical shape.

(Extrusion bearing)
5A and 5B has a shape in which a flange portion 42 protrudes from the upper end portion of the outer surface 41 of the cylindrical portion 40. The dimensions of the protruding bearing 4 are appropriately determined according to the application. In one example, the dimensions of the cylindrical portion 40 are an outer diameter of 1 cm to 3 cm, an inner diameter of 0.5 cm to 2.9 cm, a height of 0.5 cm to 3 cm, and a thickness of 1 mm to 5 mm. The dimensions of the flange portion 42 are a protrusion length of 0.2 cm to 2 cm and a thickness of 1 mm to 5 mm.

  The protruding bearing 4 includes a base body 43 and a resin layer 44.

  The base body 43 includes a base body 45 and a metal layer 46. The base body 45 and the metal layer 46 correspond to the base body 10 and the metal layer 11 of the resin coating 1 in FIG. 1, respectively.

  The resin layer 44 is for ensuring the slidability of the sliding surface (inner surface) of the protruding bearing 4. This resin layer 44 corresponds to the resin layer 11 of the resin coating 1 in FIG.

  Such a protruding bearing 4 is formed, for example, by forming a laminated body of a base body, a metal layer, and a resin layer into a disk shape with a through hole formed in the center, and subjecting this disk-shaped laminated body to an overhanging process. can get.

<Resin releasable jig>
The extrusion mold 5 shown in FIG. 6 is for forming the covered electric wire 6 by covering the core conductor 60 with the outer skin 61. This extrusion mold 5 is provided with a resin releasable jig which is an example of the resin coating.

  The extrusion mold 5 includes a die 50 and a point 51. These dies 50 and points 51 correspond to the substrate 10 of the resin coating 1 in FIG. In addition, in the dice | dies 50 and the point 51 shown in FIG. 6, the thing equivalent to the metal layer 13 in the base | substrate 10 of FIG. 1 is abbreviate | omitted.

  The die 50 has a space 52 in which the points 51 are assembled. A resin layer 54 is formed on the end face 53 of the die 50.

  The point 51 has a through hole 55 that allows the core conductor 60 to move. A resin layer 57 is formed on the end face 56 of the point 51.

  The resin layers 54 and 57 correspond to the resin layer 11 of the resin coating 1 in FIG. That is, the one in which the coating layer 54 is formed on the die 50 and the one in which the coating layer 57 is formed on the point 51 correspond to the resin releasable jig.

  In the extrusion mold 5, by assembling the points 51 in the space 52 of the die 50, a flow path 58 for supplying the resin 62 that forms the outer skin 61 is formed. The end of the flow path 58 constitutes a resin discharge port 59. Resin layers 54 and 57 exist around the resin discharge port 59.

  In the extrusion mold 5, the resin 62 discharged from the resin discharge port 59 is supplied by supplying the resin 62 to the flow path 58 while moving the core conductor 60 to the through hole 55 of the point 51 in the direction A in the figure. Can cover the outer peripheral surface of the core conductor 60 to obtain the insulated wire 6.

  In such an extrusion molding die 4, resin layers 54 and 57 excellent in releasability exist around the resin discharge port 49. For this reason, even if the resin is continuously and repeatedly discharged from the resin discharge port 59, it is possible to appropriately suppress adhesion of eyes and burrs around the resin discharge port 59.

  Further, since the surface of the die 50 and the point 51 corresponding to the substrate 10 of the resin coating 1 in FIG. 1 is roughened, the resin layers 54 and 57 have an adhesiveness to the die 50 and the point 51. Excellent. For this reason, in the extrusion mold 5, it is possible to appropriately suppress the adhesion of eyes and burrs around the resin discharge port 59 for a long period of time.

  The extrusion mold 5A shown in FIG. 7 has a resin layer 54A provided on the inner surface of a die 50 and a resin layer 57A provided on the outer surface of the point 51. In the extrusion mold 5A, the flow path 58A is defined by the resin layer 54A and the resin layer 57A.

  The resin layers 54A and 57A correspond to the resin layer 11 of the resin coating 1 in FIG. That is, each of the die 50 having the resin layer 54A and the point 51 having the resin layer 57A formed corresponds to the resin releasable jig.

  In such an extrusion mold 5 </ b> A, resin layers 54 </ b> A and 57 </ b> A having excellent releasability exist near the resin discharge port 59. For this reason, even if the resin is continuously and repeatedly discharged from the resin discharge port 59, it is possible to appropriately suppress the formation of eyes and burrs around the resin discharge port 49 for a long period of time.

[Second Embodiment]
The resin coating 7 in FIG. 8 includes a base body 70 and a resin layer 71. In this resin coating 7, the one corresponding to the base body 10 and the metal layer 11 of the resin coating 1 of FIG. 1 is formed as a single member base 70.

  The substrate 70 has irregularities on the surface layer and is entirely made of metal. As a material of the base body 70, a metal having high slidability is preferable. As such a metal, the same thing as the metal layer 13 of the resin coating 1 of FIG. 1, for example, copper, copper alloy, lead, lead alloy, aluminum, aluminum alloy etc. are mentioned.

  The arithmetic average roughness (Ra) of the surface of the substrate 70, the method for forming the unevenness, and the like are the same as those of the metal layer 13 of the resin coating 1 in FIG.

  The resin layer 71 covers the unevenness of the base body 70. The resin layer 71 corresponds to the resin layer 11 of the resin coating 1 in FIG. 1 and has the same properties, functions, and the like as the resin layer 11. The resin layer 71 can also be formed by the same material, method and the like as the resin layer 11 of FIG.

  According to such a resin coating 7, since the resin layer 71 contains a cross-linked perfluoropolymer, the resin layer 71 is excellent in slidability and wear resistance is improved. Moreover, the adhesiveness between the base | substrate 70 and the resin layer 71 is improved because the base | substrate 70 has an unevenness | corrugation. Therefore, the resin coating 7 is excellent in slidability and releasability, and has improved wear resistance and adhesion between the base 70 and the resin layer 71. Moreover, since the base 70 is formed as a single member, the manufacturing process of the resin coating 7 is simplified.

[Third Embodiment]
The sliding member 8 in FIG. 9 includes a base body 80 and a resin layer 81.

  The base body 80 has a base body 82 and a metal layer 83. The substrate 80 has irregularities on the surface. The arithmetic average roughness (Ra) of the surface of the substrate 80 is preferably 5 μm or more and 200 μm or less.

  The base body 82 is the same as the base body 12 of the resin coating 1 in FIG. 1 except that the surface is uneven. The arithmetic average roughness (Ra) of the surface of the substrate body 82 is preferably 5 μm or more and 200 μm or less, like the substrate 80.

  As a method for forming irregularities on the surface of the base body 82, for example, chemical etching, electrochemical etching, blasting, or the like can be employed.

  The metal layer 83 as a surface layer is a film-like body formed along the unevenness of the base body 82. The metal layer 83 is preferably formed to have a substantially uniform thickness so that unevenness (surface roughness) by the base body 82 is maintained. The average thickness of the metal layer 83 is, for example, 1 μm or more and 1,100 μm or less, and preferably 5 μm or more and 300 μm or less. Here, the average thickness refers to an average value of thicknesses measured at a plurality of arbitrary points (for example, 5 points). The thickness of the metal layer 83 can be calculated from, for example, a scanning electron microscope (SEM) image of the cross section of the resin coating 8.

  The material of the metal layer 83 is preferably a metal with high slidability. As such a metal, the same thing as the metal layer 13 of the resin coating 1 of FIG. 1, for example, copper, copper alloy, lead, lead alloy, aluminum, aluminum alloy etc. are mentioned.

  The resin layer 81 covers the unevenness of the base body 80. The resin layer 81 corresponds to the resin layer 11 of the resin coating 1 in FIG. 1 and has the same properties, functions, and the like as the resin layer 11. The resin layer 81 can also be formed by the same material, method, etc. as the resin layer 1 of FIG.

  According to such a resin coating 8, since the resin layer 81 contains a cross-linked perfluoropolymer, the resin layer 81 is excellent in slidability and releasability and improved in wear resistance and adhesion. ing. Moreover, the adhesiveness between the base | substrate 80 and the resin layer 81 is further improved because the base | substrate 80 has an unevenness | corrugation. Therefore, the resin coating 8 has improved slidability, releasability, wear resistance, and adhesion between the substrate 80 and the resin layer 81.

  Further, the base body 80 of the resin coating 8 is formed by covering the base body 82 with the metal layer 83 after forming the top and bottom on the base body 82. Therefore, the surface roughness of the base body 80 can be controlled even when the metal layer 83 is formed. As a result, in the resin coating 8, the size of the unevenness (surface roughness) of the base body 80 can be easily adjusted.

[Other Embodiments]
The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is not limited to the configuration of the embodiment described above, but is defined by the scope of the claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of the claims. The

  For example, the shape and arrangement of the unevenness of the illustrated substrate are schematic for explaining the present invention, and do not accurately reflect the uneven shape actually formed on the substrate. The uneven shape and the like can be appropriately changed from the illustrated example.

  In the extrusion mold 5 of FIG. 6, the resin layers 54 and 57 are formed on the end faces 53 and 56 of the die 50 and the point 51, respectively, but on either one end face of the die 50 and the point 51. Only the resin layer may be formed.

  In the extrusion mold 5A of FIG. 7, the resin layers 54A and 57A are formed on the inner surface of the die 50 and the outer surface of the point 51, respectively, but either one of the inner surface of the die 50 and the outer surface of the point 51 is formed. Only the resin layer may be formed. Further, when a resin layer is formed on the inner surface of the die 50 and / or the outer surface of the point 51, the resin layer may be selectively formed only in a region near the resin discharge port 59 on the inner surface and / or the outer surface. Good.

  The present invention is not limited to the bending bearing 3 shown in FIGS. 4A and 4B described above and the protruding bearing 4 shown in FIGS. 5A and 5B, but may be used for other applications such as a cylinder for an actuator, a piston member, and a gear pump. It can be applied to a sliding member.

  ADVANTAGE OF THE INVENTION According to this invention, in the resin coating in which the resin layer containing a fluororesin was formed in the base | substrate, adhesiveness is improved, enjoying the advantageous characteristics (for example, slidability and releasability) which a fluororesin has. be able to. Therefore, the present invention can be suitably applied to bearings, cylinders and pistons for actuators, sliding members such as gear pumps, and resin coatings such as resin releasable jigs.

DESCRIPTION OF SYMBOLS 1, 7, 8 Resin coating | cover 10,70,80 Base | substrate 11,71,81 Resin layer 12,82 Base | substrate main body 13,83 Metal layer 14 Convex part 2 Laminate 20 Base material layer 21 Metal layer 3 Rolling bearing 4 Extrusion bearing 30, 43 Substrate 31, 44 Resin layer 32, 45 Substrate body 33 Metal layer 40 Cylindrical portion 41 Outer surface 42 Flange portion 46 Metal layer 5,5A Extrusion mold 50 Die 51 Point 52 Space 53, 56 End surface 54, 54A, 57, 57A Resin layer 55 Through-hole 58, 58A Flow path 59 Resin outlet 6 Covered wire 60 Core conductor 61 Outer skin 62 Resin

Claims (7)

A substrate having irregularities, and at least a surface layer including the irregularities is made of metal, and a resin layer coated on the irregularities of the substrate;
The main component of the surface layer is copper, copper alloy, lead, lead alloy, aluminum or aluminum alloy,
A resin coating in which the resin layer contains a perfluoropolymer, and at least a part of the perfluoropolymer is crosslinked or graft-modified.   The resin coating according to claim 1, wherein the resin layer further contains an engineering plastic.   The resin coating according to claim 2, wherein at least a part of the engineering plastic and the perfluoropolymer are crosslinked or graft-modified.   The resin coating according to claim 3, wherein the crosslinking or graft modification is performed by irradiation with ionizing radiation at a temperature of at least a melting point of the perfluoropolymer.   The resin coating according to claim 4, wherein the ionizing radiation is irradiated at a temperature equal to or higher than a melting point of the engineering plastic.   The resin coating according to any one of claims 1 to 5, wherein an arithmetic average roughness (Ra) of the surface of the surface layer is 5 µm or more and 200 µm or less. The substrate has a substrate body on which the surface layer is laminated,
The resin coating according to any one of claims 1 to 6, wherein the base body is made of metal, resin, or ceramics.

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