JP2015067645A - Mixed resin composition, mixed resin molding, and mixed resin coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mixed resin composition, a mixed resin molding, and a mixed resin coated material which have improved wear resistance (mechanical strength) while obtaining advantageous properties (for example, slidability and mold releasability) which a fluororesin has.SOLUTION: In a mixed resin composition where resin particles are dispersed in a dispersion medium, the resin particles contain a perfluoropolymer and an aromatic polyether ketone, the mass ratio of the perfluoropolymer to the aromatic polyether ketone is 10:90 to 90:10, and the content of the resin particles having a diameter of less than 1 μm is 20 mass% or more. Preferably, the resin particles comprise first resin particles whose main component is the perfluoropolymer, and second resin particles whose main component is the aromatic polyether ketone. A mixed resin coated material includes a substrate and a mixed resin molding formed of the mixed resin composition on at least a part of the substrate.

Description

  The present invention relates to a mixed resin composition, a mixed resin molded body, and a mixed 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. Examples of products coated with fluororesin (fluorine resin coating) include sliding products such as bearings in addition to household products such as inner pots such as rice cookers and home bakery, electric pans, hot plates and pans 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. Thus, it has been proposed to improve the wear resistance of the fluororesin by irradiating the fluororesin with ionizing radiation to cause a crosslinking reaction (for example, JP2013-027875A, JP2011-074938A). Gazette, 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 (hereinafter also referred to as “crosslinked fluororesin”) has improved wear resistance as compared to an uncrosslinked fluororesin. However, in applications where high wear resistance is required, the wear resistance may be insufficient even with a cross-linked fluororesin. Therefore, there is still room for improvement with respect to the wear resistance of the cross-linked fluororesin.

  The present invention has been made based on the above circumstances, and is a mixed resin composition that improves the abrasion resistance while enjoying the advantageous properties (for example, slidability and releasability) possessed by the fluororesin. It is an object to provide a molded article, a mixed resin molded body, and a mixed resin coating.

  The present invention is a mixed resin composition in which resin particles are dispersed in a dispersion medium, wherein the resin particles include a perfluoropolymer and an aromatic polyetherketone, and the perfluoropolymer and the aromatic polyetherketone The mixed resin composition has a mass ratio of 10:90 or more and 90:10 or less, and the content of resin particles having a particle size of less than 1 μm among the resin particles is 20% by mass or more.

  Another aspect of the present invention is a mixed resin molded body formed by irradiating a coating film obtained by coating and drying the mixed resin composition with ionizing radiation.

  Yet another aspect of the present invention includes a perfluoropolymer and an aromatic polyetherketone, wherein the mass ratio of the perfluoropolymer to the aromatic polyetherketone is 10:90 or more and 90:10 or less, and irradiation with ionizing radiation. This is a mixed resin molded body in which chemical bonds are formed.

  Yet another aspect of the present invention is a mixed resin coating comprising a base material and the mixed resin molded body formed on at least a part of the outer surface of the base material.

  Yet another aspect of the present invention is a mixed resin coating comprising a metal substrate and the mixed resin molded body formed on at least a part of the outer surface of the metal substrate.

  According to the present invention, there are provided a mixed resin composition, a mixed resin molded body, and a mixed resin coating that are improved in wear resistance while enjoying advantageous properties (for example, slidability and releasability) possessed by a fluororesin. Provided.

It is typical sectional drawing which shows the mixed resin coating material of this invention. It is a typical perspective view which shows the bending bearing which is an example of the mixed resin coating material of this invention. It is typical sectional drawing which follows the X1-X1 line | wire of FIG. It is typical sectional drawing which follows the X2-X2 line | wire of FIG. It is a typical perspective view which shows the extrusion bearing which is the other example of the mixed resin coating material of this invention. It is typical sectional drawing which follows the X3-X3 line | wire of FIG. It is typical sectional drawing which shows the metal mold | die for extrusion molding provided with the mold release jig | tool which is another example of the mixed resin coating material of this invention. It is typical sectional drawing which shows the metal mold | die for extrusion molding provided with the mold release jig | tool which is another example of the mixed resin coating material of this invention. It is a schematic diagram for demonstrating the thrust abrasion test in an Example.

[Description of Embodiment of the Present Invention]
The present invention made to solve the above-mentioned problems is a mixed resin composition in which resin particles are dispersed in a dispersion medium, wherein the resin particles contain a perfluoropolymer and an aromatic polyetherketone, and the perfluoropolymer Resin composition having a mass ratio of 10:90 to 90:10 and a resin particle content of less than 1 μm among the resin particles is 20% by mass or more. It is.

  Since the mixed resin composition contains a perfluoropolymer and an aromatic polyether ketone, the coating film formed by the mixed resin composition has a slidability, a releasability, etc. that the perfluoropolymer has. It is possible to have both the characteristics such as excellent properties, the abrasion resistance of the aromatic polyether ketone, and the properties such as excellent adhesion between the coating film and the object to be coated.

  In particular, by setting the mass ratio of the perfluoropolymer and the aromatic polyether ketone to 10:90 or more and 90:10 or less, even when the perfluoropolymer and the aromatic polyether ketone are mixed, the perfluoropolymer It can suppress that the outstanding characteristic which a polymer has, and the outstanding characteristic which an aromatic polyether ketone has fallen.

  Further, the mixed resin composition is compared with a coating film formed by the mixed resin composition because the content of the resin particles having a particle size of less than 1 μm among the resin particles is 20% by mass or more. The possibility that a resin particle or a resin particle lump having a large target particle size remains is reduced. Therefore, since the possibility that the resin particles and the like are detached when the coating film or the like is rubbed (slid), the durability can be improved and the life can be extended.

  The resin particles may be composed of first resin particles mainly containing the perfluoropolymer and second resin particles mainly containing the aromatic polyether ketone. Thereby, adjustment of the mass ratio between the perfluoropolymer and the aromatic polyether ketone is facilitated by adjusting the blending ratio of the first resin particles and the second resin particles. As a result, it becomes easy to adjust the properties of the coating film formed by the mixed resin composition.

  Another aspect of the present invention made to solve the above-mentioned problems is a mixed resin molded body formed by irradiating a coating film obtained by coating and drying the mixed resin composition with ionizing radiation.

  Since the mixed resin molded body is obtained by the mixed resin composition, the perfluoropolymer has excellent slidability, releasability and the like, and the aromatic polyether ketone has excellent wear resistance and the like. It can have both properties.

  Moreover, the said mixed resin molding is formed by irradiating the said coating film with ionizing radiation. When the coating film is irradiated with ionizing radiation, a chemical bond may be formed on at least a part of the perfluoropolymer and the aromatic polyether ketone. Since the bonds between the polymers by chemical bonds are covalent bonds or hydrogen bonds, they are stronger than the intermolecular cohesive force of the fluororesin. Therefore, in the mixed resin molded body, the polymers can be bonded more firmly. As a result, in the mixed resin molded body, in addition to containing the aromatic polyether ketone, it is possible to improve mechanical strength and improve wear resistance by forming a chemical bond.

  Yet another aspect of the present invention made to solve the above problems includes a perfluoropolymer and an aromatic polyetherketone, wherein the mass ratio of the perfluoropolymer to the aromatic polyetherketone is 10:90 or more and 90: It is a mixed resin molded body having a chemical bond formed by irradiation with ionizing radiation.

  Since the mixed resin molded body contains a perfluoropolymer and an aromatic polyether ketone, the perfluoropolymer has excellent characteristics such as slidability and releasability, and the wear resistance of the aromatic polyether ketone. It is possible to combine the characteristics such as excellent properties.

  In particular, when the mass ratio of the perfluoropolymer to the aromatic polyether ketone is 10:90 or more and 90:10 or less, even when the perfluoropolymer and the aromatic polyether ketone are mixed, the perfluoropolymer It is possible to suppress deterioration of the excellent characteristics of the polymer and the excellent characteristics of the aromatic polyether ketone.

  Further, since the mixed resin molded body has a chemical bond formed by irradiation with ionizing radiation, it further improves the mechanical strength and wear resistance in addition to the effect of containing the aromatic polyether ketone. be able to.

  The ionizing radiation may be irradiated at a temperature equal to or higher than the melting point of the perfluoropolymer and the aromatic polyether ketone. By performing ionizing radiation irradiation at a temperature higher than the melting point of these resins, chemical bonds in the mixed resin molded body can be appropriately formed. As a result, the mixed resin molded body can be improved in mechanical strength and wear resistance more appropriately.

  The mixed resin molded body may be a film. Thus, since the said mixed resin molding is a film form, it can be easily coat | covered with a mixed resin molding with respect to the coating target object of various shapes. Therefore, it is possible to form a resin coating layer formed from the mixed resin composition on the coating target even when it is difficult to form a coating film with the mixed resin composition on the coating target. Become.

  Still another aspect of the present invention made to solve the above problems is a mixed resin coating comprising a base material and the mixed resin molded body formed on at least a part of the outer surface of the base material.

  According to the mixed resin coating, since the mixed resin molded body is formed from the mixed resin composition, it is possible to enjoy the effects of the mixed resin molded body. Specifically, the properties such as perfluoropolymer have excellent slidability, releasability, etc., the aromatic polyetherketone has excellent wear resistance, the mixed resin molded article has excellent adhesion to the substrate, etc. It becomes possible to have both characteristics. In addition, it is possible to obtain an effect of improving the wear resistance by forming a chemical bond and an effect of improving the adhesion between the resin molded body and the substrate. As a result, the mixed resin coating is excellent in slidability, releasability, wear resistance, adhesion, and the like.

  Yet another aspect of the present invention made to solve the above problems is a mixed resin coating comprising a metal substrate and the mixed resin molded body formed on at least a part of the outer surface of the metal substrate.

  According to the mixed resin coating, since the mixed resin molded body is formed from the mixed resin composition, it is possible to enjoy the effects of the mixed resin molded body. Specifically, it has excellent properties such as slidability and releasability of the perfluoropolymer, abrasion resistance of the aromatic polyether ketone, and excellent adhesion of the mixed resin molding to the metal substrate. It is possible to have both of these characteristics. In addition, it is possible to obtain an effect of improving the wear resistance by forming a chemical bond and an effect of improving the adhesion between the resin molded body and the substrate. As a result, the mixed resin coating is excellent in slidability, releasability, wear resistance, adhesion, and the like.

  It is preferable that at least an outer surface of the metal base material on which the mixed resin molded body is formed is roughened by etching. Thus, the adhesiveness of the said mixed resin molding with respect to a base material can be improved more appropriately because the outer surface of a base material is roughened. Further, in sliding applications, it is preferable because the bonding surface area with the base material is increased, so that the thermal conductivity to the base material is improved and the durability limit such as the limit PV value is improved.

  Here, the “particle diameter” is a value measured by a gravity sedimentation method. The content of the resin particles having a particle size of less than 1 μm can be calculated from the mass-based particle size distribution based on the input mass of the resin particles at the time of preparing the mixed resin composition. The “main component” is a component having the largest content, for example, a component containing 50% by mass or more. “Chemical bond” refers to a covalent bond or a hydrogen bond. “Etching” includes physical processing such as blasting in addition to chemical etching and electrochemical etching. The “mixed resin molded product” is not limited to a single material such as a film, but also includes a resin coating layer formed on a substrate by coating or the like and integrated with the substrate or the like. 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 mixed resin composition, the mixed resin molded body, and the mixed resin coating of the present invention will be described.

[Mixed resin composition]
The mixed resin composition is obtained by dispersing resin particles in a dispersion medium. The said mixed resin composition may contain the other resin component and arbitrary components in the range which does not impair the effect of this invention.

<Resin particles>
The resin particles contain a perfluoropolymer and an aromatic polyether ketone. The resin particles are preferably composed of first resin particles whose main component is perfluoropolymer and second resin particles whose main component is aromatic polyetherketone. Thereby, adjustment of the characteristic of a perfluoropolymer and aromatic polyether ketone becomes easy by adjusting the compounding ratio of the 1st resin particle and the 2nd resin particle.

  The lower limit of the content of the resin particles having a particle size of less than 1 μm in the resin particles is 20% by mass, preferably 50% by mass, and more preferably 80% by mass or more. On the other hand, the upper limit of the content is preferably 100% by mass.

  By forming a mixed resin molded body (resin coating layer) using the mixed resin composition containing such resin particles, advantageous properties (excellent slidability, etc.) of perfluoropolymer and aromatic polyether It is possible to have the advantageous properties (excellent abrasion resistance, etc.) of the ketone while suppressing the decrease in the advantageous properties due to the combined use of these resins. For example, when a pulverized powder with a large content of resin particles having a large particle size is used as the resin particles, the mixed resin molded body (resin coating layer) has insufficient expression of characteristics such as slidability and wear resistance. There is a risk. Moreover, since resin particles or resin particle blocks having a large particle size of about several μm to several tens of μm are easily dropped during friction, durability (life) may be reduced. On the other hand, by using the mixed resin composition in which the content of particles having a particle size of less than 1 μm is not less than the above lower limit, surprisingly advantageous properties of perfluoropolymer (excellent slidability, etc.) ) And the advantageous properties (excellent wear resistance, etc.) of aromatic polyether ketones have been found to be significantly improved.

  Specifically, as a result of intensive studies by the present inventors, a dispersion of polytetrafluoroethylene (PTFE) having an average particle diameter (median diameter) of 0.2 μm as a perfluoropolymer and an average particle diameter of 0.2 μm. The resin molded product produced by ionizing radiation irradiation using a mixed dispersion with a dispersion of aromatic polyether ketone has a mass ratio of perfluoropolymer to aromatic polyether ketone of 10:90 or more and 90:10 or less. Occasionally excellent releasability, slidability and wear resistance.

  On the other hand, if the mass ratio of the perfluoropolymer and the aromatic polyether ketone deviates from the above range, either of the characteristics of the perfluoropolymer and the aromatic polyether ketone is not sufficiently expressed, and the practical slidability, Abrasion resistance cannot be obtained. Thus, by making the mass ratio in the above range, it is possible to suppress the deterioration of the properties of the perfluoropolymer and the aromatic polyetherketone in the coating film formed from the mixed resin composition, and the superiority of those resins. Characteristics can be developed. In order to obtain such an effect more reliably, the mass ratio is preferably 20:80 or more and 80:20, and more preferably 35:65 or more and 65:35. 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 each of the characteristics of the perfluoropolymer and the aromatic polyether ketone is 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 aromatic polyether ketone, and the characteristics of the perfluoropolymer may be expressed predominately. On the other hand, when emphasizing the mechanical strength (wear resistance) and the adhesion between the above-mentioned coating film and the like and the material to be coated such as this coating film, the mass of the aromatic polyether ketone is larger than the mass of the perfluoropolymer. In addition, the characteristics of the aromatic polyether ketone may be expressed predominantly.

  The content of particles having a particle size of less than 1 μm among the resin particles is 20% by mass or more, preferably 50% by mass or more, and more preferably 80% by mass or more. When the content is 20% by mass or more, advantageous characteristics of the perfluoropolymer and the aromatic polyether ketone are expressed.

(Perfluoropolymer)
The perfluoropolymer mainly improves the slidability of the mixed resin molded body obtained from the mixed resin composition. Here, the perfluoropolymer is a polymer that does not contain a hydrogen atom composed of carbon atoms and fluorine atoms, or an atom other than carbon atoms and fluorine atoms (for example, oxygen) 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.

(Aromatic polyether ketone)
The aromatic polyether ketone mainly improves the scratch resistance and hardness of the mixed resin molded body obtained from the resin composition, and the wear resistance including these. This aromatic polyetherketone has a structure in which the benzene rings are bonded to the para position and the benzene rings are connected to each other by a rigid ketone bond (-C = O) or a flexible ether bond (-O-). Resin. Examples of the aromatic polyether ketone include ether ether ketone (PEEK), ether bond, and benzene ring having structural units in which an ether bond, a benzene ring, an ether bond, a benzene ring, a ketone bond, and a benzene ring are arranged in this order. , Polyether ketone (PEK) having a structural unit in which a ketone bond and a benzene ring are arranged in this order. Among them, PEEK is preferable as the aromatic polyether ketone. Since such aromatic polyether ketone is excellent in wear resistance, heat resistance, insulation, workability, etc., a mixed resin molded article or mixed resin coating containing aromatic polyether ketone is a base material. Excellent bondability with other materials.

  A commercially available product can be used as the aromatic polyether ketone such as PEEK. As aromatic polyether ketones such as PEEK, those of various grades are commercially available. A single grade of aromatic polyether ketone that is commercially available may be used alone, or multiple grades of aromatic polyether ketone may be used. An aromatic polyether ketone may be used in combination, or a modified aromatic polyether ketone may be used.

(Other resin components)
Examples of the other resin component include an adhesive component having higher adhesion to the substrate than perfluoropolymer and aromatic polyether ketone. Such a mixed resin composition containing an adhesive component can be prepared, for example, by dispersing perfluoropolymer and aromatic polyetherketone resin particles in an aqueous dispersion of an adhesive component or an organic solvent solution.

  The lower limit of the mass ratio of the adhesive component in the total mass of the main resin particles (perfluoropolymer and aromatic polyetherketone resin particles) and the adhesive component is preferably 1% by mass, and more preferably 5% by mass. As an upper limit of this mass ratio, 20 mass% is preferable and 10 mass% is more preferable. There exists a possibility that adhesiveness cannot fully be improved as the mass ratio of an adhesive component is less than the said minimum. On the other hand, when the content of the adhesive component exceeds the above upper limit, the content of the perfluoropolymer and the aromatic polyether ketone is relatively small, so that the slidability and the wear resistance may be lowered.

(Optional component)
Examples of the optional component include a crosslinking aid. PTFE, PEEK, etc. are materials having excellent flame retardancy, and usually it is not necessary to add a flame retardant. However, if it is necessary for special usage, use a conventional flame retardant for resin flame retardant blending. It does not interfere with blending at the blend ratio of normal use.

  Examples of the crosslinking aid include triallyl isocyanate (TAIC), diallyl isocyanate, di (meth) acryl isocyanate, tri (meth) acryl isocyanurate, 1,4-butanediol di (meth) acrylate, polyethylene glycol di (meth). Examples include acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate, divinylbenzene, trivinylbenzene, and hexamethylbenzene.

<Dispersion medium>
Examples of the dispersion medium include water, an organic solvent, a mixed solvent thereof, and the like. Among these, water is preferable. As an organic solvent, the solubility of aromatic polyether ketones such as perfluoropolymer and PEEK in this organic solvent is low, and the content of resin particles having a particle size of less than 1 μm among the resin particles is 20% by mass or more. What can be maintained is preferred.

<Advantages>
Since the mixed resin composition contains a perfluoropolymer and an aromatic polyether ketone such as PEEK, the coating film formed by the mixed resin composition has a sliding property and a release property that the perfluoropolymer has. It is possible to have both the properties such as excellent properties and the wear resistance of the aromatic polyether ketone, and the properties such as excellent adhesion between the coating film and the object to be coated.

  In particular, by setting the mass ratio of the perfluoropolymer and the aromatic polyether ketone to 10:90 or more and 90:10 or less, even when the perfluoropolymer and the aromatic polyether ketone are mixed, the perfluoropolymer It can suppress that the outstanding characteristic which a polymer has, and the outstanding characteristic which an aromatic polyether ketone has fallen.

  Further, the mixed resin composition is compared with a coating film formed by the mixed resin composition because the content of the resin particles having a particle size of less than 1 μm among the resin particles is 20% by mass or more. The possibility that a resin particle or a resin particle lump having a large target particle size remains is reduced. Therefore, the possibility that the resin particles and the like are detached when the coating film or the like is rubbed (slided) is reduced, so that durability (life) is improved.

[Mixed resin molding]
In one example, the mixed resin molded body is formed by irradiating a coating film obtained by coating and drying the mixed resin composition with ionizing radiation (hereinafter referred to as “mixed resin molded body (1)”). Also called).

  In another example, the mixed resin molded body includes a perfluoropolymer and an aromatic polyether ketone such as PEEK, and the mass ratio of the perfluoropolymer to the aromatic polyether ketone is 10:90 or more and 90:10 or less. In other words, chemical bonds are formed by irradiation with ionizing radiation (hereinafter also referred to as “mixed resin molding (2)”). As with the mixed resin molded body (1), the mixed resin molded body (2) is preferably formed by irradiating a coating film obtained by coating and drying the mixed resin composition with ionizing radiation.

(Coating)
Application of the mixed resin composition can be performed 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, and a spray coating method.

(Dry)
As long as the dispersion medium can be evaporated, drying of the mixed resin composition may be either natural drying or forced drying, 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)
The ionizing radiation irradiation is performed in order to form a chemical bond in at least a part of the coating film. 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 irradiating the coating film with ionizing radiation, a chemical bond is formed in at least a part of the perfluoropolymer and the aromatic polyether ketone in the coating film.

  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 output electron beam can be obtained, and the degree of chemical bond formation 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, chemical bond formation may be insufficient and sufficient wear resistance may not be obtained. On the other hand, when the irradiation dose of ionizing radiation exceeds the above upper limit, the balance between the formation of chemical bonds of the resin in the coating film and the decomposition of the resin (breaking of the main chain) becomes an equilibrium state, and the processing efficiency decreases, or There is a possibility that the resin is excessively decomposed and wear resistance is lowered. On the other hand, when the irradiation dose is 50 to 800 kGy, the formation of chemical bonds of the resin proceeds sufficiently and the resin is hardly decomposed, so that sufficient wear resistance can be obtained. Therefore, by setting the irradiation dose within the above range, the mixed resin molded body more appropriately has properties such as releasability, slidability, and wear resistance.

  The ionizing radiation irradiation is preferably performed in a low oxygen or oxygen-free atmosphere as described above. By performing ionizing radiation irradiation in such an atmosphere, for example, when the mixed resin molded bodies (1) and (2) are formed on the coating target (base material), the mixed resin molded bodies (1) and (1 2) The adhesive force between the covering object (base material) 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.

  Further, by setting the oxygen concentration to 500 ppm or less, more preferably 100 ppm or less, and even more preferably 10 ppm or less, the resin is decomposed by ionizing radiation, the formation of chemical bonds of the resin, and the resin and the coating object (base material). In the competitive reaction with the adhesion of the resin, the formation of the chemical bond of the resin and the reaction of the adhesion are remarkably dominant.

  Furthermore, 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 near or higher than the melting points of the perfluoropolymer and the aromatic polyether ketone, preferably 80 ° C. or higher, more preferably 40 ° C. or lower. For example, when the perfluoropolymer is PTFE and PEEK is an aromatic polyether ketone, the melting point of PTFE is 327 ° C., and the melting point of PEEK is 334 ° C., so that the heating temperature is 344 ° C. to 367 ° C. It is preferable. By performing the heating temperature at a temperature higher than the melting point of the resin, formation of the chemical bond of the resin can be appropriately promoted. On the other hand, by setting the upper limit of the heating temperature to not more than 80 ° C. higher than the melting point of the resin, it is possible to suppress the thermal decomposition (breaking of the main chain) of the resin and to suppress the deterioration of the slidability and wear resistance. .

  The mixed resin molded bodies (1) and (2) may be formed as a film-shaped mixed resin film. The mixed resin film can be obtained by forming a chemical bond on the resin film intermediate by ionizing radiation after forming the resin film intermediate.

  The resin film intermediate can be formed, for example, by removing the coating material after forming a coating film on the coating material using the mixed resin composition. The coating film is formed by coating the mixed resin composition on the material to be coated and then evaporating the dispersion medium by drying. Examples of the method for removing the material to be coated include mechanical peeling and chemical treatment. As a chemical | medical agent process, when forming a to-be-coated material with metal foil, such as aluminum foil, the method of melt | dissolving and removing aluminum foil etc. with an acid etc. is mentioned, for example.

  Another method for forming the resin film intermediate is to form a dry product of the mixed resin composition by melt rolling or ram extrusion, and then forming the film by roll rolling or stretching, if necessary, followed by free sintering as necessary. The method of baking with is mentioned.

  This mixed resin film can be easily coated with the mixed resin moldings (1) and (2) on the objects to be coated having various shapes. Therefore, it is possible to form a resin coating layer formed from the mixed resin composition on the coating target even when it is difficult to form a coating film with the mixed resin composition on the coating target. Become.

<Advantages>
Since the mixed resin molded body contains a perfluoropolymer and an aromatic polyether ketone, the perfluoropolymer has excellent characteristics such as slidability and releasability, and the wear resistance of the aromatic polyether ketone. It is possible to have properties such as excellent properties, mechanical strength, adhesion to a coating object (base material), and the like. Further, the mixed resin molded body is further improved in wear resistance and mechanical strength because a chemical bond is formed by irradiation with ionizing radiation.

[Mixed resin coating]
The mixed resin coating 1 in FIG. 1 is obtained by forming a resin coating layer 11 as the mixed resin molded body on at least a part of the outer surface of the substrate 10. Examples of the mixed resin coating include resin releasable jigs such as bearings, extrusion die heads and die of extrusion molds, cylinders and piston members for actuators, gear pumps, and the like.

(Base material)
The material of the substrate 10 is not particularly limited as long as it has good adhesion to the resin coating layer 11 and has the desired strength, and examples thereof include metals, plastics such as polyimide, ceramics, and glass. Among them, metal is preferable. 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.

  As the base material 10, surface treatment may be applied to at least a part of the outer surface (a region where the resin coating layer 11 is to be formed). Examples of the surface treatment include rust prevention treatment, scratch resistance treatment, primer treatment, and surface roughening treatment.

  The rust prevention treatment is a treatment for preventing the outer surface of the base material 10 from being oxidized. The scratch resistance process is a process for preventing damage to the outer surface of the substrate 10. Examples of the rust prevention treatment and scratch resistance treatment include a method of forming a coating layer such as a metal oxide layer or an alloy layer.

  The primer treatment is a treatment for improving the adhesion of the resin coating layer 11 to the substrate 10. Examples of the primer treatment include a method of forming a primer layer on the outer surface of the base material 10 with a resin (adhesive component) having higher adhesion to the base material 10 than the perfluoropolymer, for example, polyamideimide or polyether sulfone.

  The roughening treatment is a treatment for improving the adhesion between the base material 10 and the resin coating layer 11. As the surface roughness of the outer surface of the substrate 10 in the case of performing the roughening treatment, the arithmetic average roughness Ra is preferably 5 μm or more and 200 μm or less. There exists a possibility that the adhesive force of the base material 10 and the resin coating layer 11 cannot fully be raised as the said arithmetic mean roughness Ra is less than the said minimum. When the arithmetic average roughness Ra exceeds the above upper limit, when the resin coating layer 11 is formed on the base material 10, pinholes are easily generated in the resin coating layer 11, and between the base material 10 and the resin coating layer 11. There is a risk that it is difficult to sufficiently increase the adhesive force. Here, the arithmetic average roughness Ra is a value measured according to JIS B 0601: 2001.

  As the roughening treatment, 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 outer surface of the substrate 20. 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 outer surface of the substrate 10.

The electrochemical etching is performed, for example, by applying alternating current, pulse current, or half-wave rectification to the substrate 10 in a state where the substrate 10 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. By setting the electrochemical etching conditions as described above, the outer surface of the substrate 10 can be finely roughened.

  As the surface roughening treatment, a method other than the chemical treatment and the electrochemical treatment can be adopted as long as the outer surface of the base material 10 can be roughened to a desired roughness. Examples of such roughening treatment include physical treatment such as sand blasting, grid blasting, and shot blasting.

(Resin coating layer)
The resin coating layer 11 corresponds to an example of the resin molded body. The resin coating layer 11 includes at least an aromatic polyether ketone such as a perfluoropolymer and PEEK, and other resin components other than the perfluoropolymer and the aromatic polyether ketone as long as the effects of the present invention are not impaired. Optional components may be included. The perfluoropolymer, aromatic polyether ketone, other resin components, and optional components are the same as those of the resin composition described above.

  The mass ratio of the perfluoropolymer to the aromatic polyether ketone in the resin coating layer 11 is preferably 10:90 or more and 90:10 or less, more preferably 20:80 or more and 80:20 or less, and 35:65 or more and 65:35. The following is more preferable. If the mass ratio between the perfluoropolymer and the aromatic polyetherketone deviates from the above range, any of the characteristics of the perfluoropolymer and the aromatic polyetherketone will not be sufficiently exhibited, and practical slidability and wear resistance There is a possibility that the properties and the like cannot be obtained. On the other hand, by setting the mass ratio in the above range, the resin coating layer 11 can have both the excellent characteristics of the perfluoropolymer and the excellent characteristics of the aromatic polyether ketone.

  What is necessary is just to determine the thickness of the resin coating layer 11 suitably according to the dimension, use, etc. of the base material 10. FIG. The thickness of the resin coating layer 11 is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less. If the thickness of the resin coating layer 11 is less than the lower limit, the adhesion and durability of the resin coating layer 11 may be reduced, and the life may be shortened. On the other hand, if the thickness of the resin coating layer 11 exceeds the above upper limit, cracks are likely to occur, and chemical bond formation due to irradiation of ionizing radiation is insufficient, and the effect of improving wear resistance cannot be sufficiently obtained. There is a fear.

  Next, a bearing, which is a typical example of the mixed resin coating, and a resin releasable jig will be described with reference to the drawings. About a bearing, a winding bearing and a protrusion bearing are demonstrated. In addition, below, the overlapping description about the matter demonstrated in the said mixed resin composition and the said mixed resin molded object may be abbreviate | omitted.

<Winding bearing>
2 to 4 is formed in a substantially cylindrical shape as a whole. The wound bearing 2 includes a substantially cylindrical base material 20 and a resin coating layer 21 formed on the inner surface of the base material 20.

  The dimension of the winding bearing 2 is appropriately determined according to the application. In one example, the winding bearing 2 has dimensions of an outer diameter of 0.4 cm to 3 cm, an inner diameter of 0.2 cm to 2.9 cm, a height of 0.2 cm to 3 cm, and a thickness of 0.2 mm to 5 mm.

  The base material 20 constitutes the core of the wound bearing 2 and is formed in a substantially cylindrical shape. This base material 20 corresponds to the base material 10 of the mixed resin coating 1 of FIG.

  The resin coating layer 21 is for ensuring the sliding property of the sliding surface (inner surface) in the bending bearing 2. This resin coating layer 21 is an example of the resin molded body, and corresponds to the resin coating layer 11 of the mixed resin coating 1 in FIG.

  Such a bending bearing 2 can be obtained, for example, by bending a strip-shaped mixed resin coating formed on a flat plate into a cylindrical shape.

<Extrusion bearing>
5 and 6 has a shape in which a flange portion 31 protrudes from the upper end portion of the outer surface 30A of the cylindrical portion 30. As shown in FIG. The protruding bearing 3 includes a base material 32 and a resin coating layer 33.

  The dimension of the protruding bearing 3 is appropriately determined according to the application. In one example, the dimensions of the cylindrical portion 30 are such that the outer diameter is 0.4 cm to 3 cm, the inner diameter is 0.2 cm to 2.9 cm, the height is 0.2 cm to 3 cm, and the thickness is 1 mm to 5 mm. The flange portion 31 has a protrusion length of 0.2 cm to 2 cm and a thickness of 0.2 mm to 5 mm.

  The base material 32 constitutes the core of the protruding bearing 3. The base material 32 has a cylindrical portion 34 and a flange portion 35. This base material 32 corresponds to the base material 10 of the mixed resin coating 1 of FIG.

  The resin coating layer 33 is for ensuring the slidability of the sliding surface (inner surface) of the protruding bearing 3. This resin coating layer 33 is an example of the resin molded body, and corresponds to the resin coating layer 11 of the mixed resin coating 1 in FIG.

  Such a protruding bearing 3 can be obtained, for example, by subjecting a mixed resin coating material in which a resin coating layer is formed on a disk-shaped base material having a through-hole formed in the central portion thereof to an overhanging process.

<Resin releasable jig>
The extrusion mold 4 shown in FIG. 7 is for forming the covered electric wire 5 by covering the core conductor 50 with the outer skin 51. This extrusion mold 4 includes a resin releasable jig that is an example of the mixed resin coating.

  The extrusion mold 4 includes a die 40 and a point 41. These dies 40 and points 41 correspond to the base material 10 of the mixed resin coating 1 of FIG.

  The die 40 has a space 42 in which the point 41 is assembled. A resin coating layer 44 is formed on the end face 43 of the die 40.

  The point 41 has a through hole 45 that allows the core conductor 50 to move. A resin coating layer 47 is formed on the end face 46 of the point 41.

  The resin coating layers 44 and 47 correspond to the resin coating layer 11 of the mixed resin coating 1 in FIG. That is, each of the die 40 with the resin coating layer 44 formed thereon and the point 41 with the resin coating layer 47 formed thereon correspond to the resin releasable jig.

  In the extrusion mold 4, the point 41 is assembled in the space 42 of the die 40, thereby forming a flow path 48 for supplying the resin 52 that forms the outer skin 51. The end of the flow path 48 constitutes a resin discharge port 49. Resin coating layers 44 and 47 exist around the resin discharge port 49.

  In the extrusion mold 4, the resin 52 discharged from the resin discharge port 49 is supplied by supplying the resin 52 to the flow path 48 while moving the core conductor 50 to the through-hole 45 of the point 41 in the direction A in the figure. Can cover the outer peripheral surface of the core conductor 50 to obtain the insulated wire 5.

  In such an extrusion mold 4, resin coating layers 44 and 47 having excellent releasability exist around the resin discharge port 49. Therefore, even if the resin is continuously and repeatedly discharged from the resin discharge port 49, it is possible to appropriately suppress the adhesion of eyes and burrs around the resin discharge port 49.

  The extrusion mold 4 </ b> A in FIG. 8 is provided with a resin coating layer 44 </ b> A on the inner surface of the die 40 and a resin coating layer 47 </ b> A on the outer surface of the point 41. In the extrusion mold 4A, the flow path 48A is defined by the resin coating layer 44A and the resin coating layer 47A.

  The resin coating layers 44A and 47A correspond to the resin coating layer 11 of the mixed resin coating 1 in FIG. That is, the one in which the resin coating layer 44A is formed on the die 40 and the one in which the resin coating layer 47A is formed on the point 41 correspond to the resin releasable jig.

  In such an extrusion mold 4A, resin coating layers 44A and 47A having excellent releasability exist in the vicinity of the resin discharge port 49. Therefore, even if the resin is continuously and repeatedly discharged from the resin discharge port 49, it is possible to appropriately suppress the adhesion of eyes and burrs around the resin discharge port 49.

<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

  In the extrusion mold 4 of FIG. 7, the resin coating layers 44 and 47 are formed on the end surfaces 43 and 46 of the die 40 and the point 41, respectively, but the resin coating layer is formed on one end surface of the die 40 and the point 41. May be formed.

  In the extrusion mold 4A of FIG. 8, the resin coating layers 44A and 47A are formed on the inner surface of the die 40 and the outer surface of the point 41, respectively. However, one of the inner surface of the die 40 and the outer surface of the point 41 is coated with resin. A layer may be formed. Further, when the resin coating layer is formed on the inner surface of the die 40 and the outer surface of the point 41, the resin coating layer may be formed only in a region near the discharge port 49 on the inner surface or the outer surface.

  The present invention is not limited to the above-described bending bearing 2 in FIGS. 2 to 4, the protruding bearing 3 in FIGS. 5 and 6, and the resin mold releasable jig of the extrusion mold 4 in FIG. In addition to the above-mentioned mixed resin coatings, for example, sliding members such as cylinders and piston members for actuators, gear pumps, etc., the present invention can be applied to various applications that require slidability, wear resistance, releasability and the like.

  Below, this invention is demonstrated based on an Example and a comparative example. In addition, this invention is not limited to these Examples, These Examples can be changed and changed based on the meaning of this invention, and they are excluded from the scope of the present invention. is not.

<Example 1>
As a base material, a disk having a diameter of 360 mm and a thickness of 1.7 mm formed from an aluminum alloy (JIS-3003; Al—Mn alloy) was used. An aluminum disk was used as an anode, and electrochemical etching was performed in an aqueous ammonium chloride solution with an amount of electricity of 25 C / cm ² to form fine irregularities on the surface of the aluminum disk.

  PTFE dispersion ("DK3700" from Daikin) and PEEK dispersion ("PEEK F804" from Victrex) were mixed so that the mass ratio of PTFE to PEEK was 10:90, and 1 μm in all resin particles A mixed dispersion having a ratio of less than resin particles of 98% by mass was obtained. The mixed dispersion is spin-coated on a surface-treated aluminum alloy (base material), dried, and held in a heating furnace maintained at 340 ° C. for 20 minutes to sinter the mixed dispersion to form a substrate. A resin coating layer having a thickness of 25 μm was obtained.

  The base material having the resin coating layer was placed on a hot plate adjusted to a temperature of 270 ° C., and the hot plate was conveyed by a conveyor belt to an irradiation region of a conveyor type electron beam irradiation apparatus (NHV Corporation). In the chamber of the electron beam irradiation apparatus, a nitrogen gas having an oxygen concentration of 0.1 ppm was flowed to maintain the oxygen concentration in the irradiation region at 3.4 ppm. An electron beam with an acceleration voltage of 1.16 MeV was irradiated from above the PTFE layer so that the irradiation dose was 60 kGy to form a chemical bond in PTFE of the resin coating layer, thereby obtaining a resin coating. The thickness of the resin coating layer after the chemical bond formation was 26 μm.

<Examples 2 to 4 and Comparative Examples 1 to 4>
A resin coating was formed in the same manner as in Example 1 except that the ratio of the resin particles less than 1 μm and the mass ratio of the PTFE dispersion and the PEEK dispersion were changed as shown in Table 1.

<Evaluation>
About the resin coating body of Examples 1-5 and Comparative Examples 1-4, the measurement of the pencil hardness, the thrust rotation abrasion test, and the cross cut test were done. The evaluation results are shown in Table 1. In Table 1, the limit PV value calculated from the result of the thrust rotating wear test and the comprehensive evaluation are shown simultaneously. The overall evaluation in Table 1 was determined according to the following criteria.

A: Suitable as a sliding member B: Limit of application as a sliding member C: Not applicable as a sliding member

(Measurement of pencil hardness)
The pencil hardness was measured as the hardness of the pencil at which the scratch was visible when the substrate was scratched with a pencil at a temperature of 30 ° C.

(Thrust wear test)
As shown in FIG. 9, the resin coating 6 in which the resin coating layer 61 is formed on the base material 60 is screwed onto the fixing member 70 in the base material 60 and fixed so that the resin coating 6 does not rotate. An abrasive 71 (“Scotch Bright # 3000” from 3M) and a 2 kg weight 72 were placed on the coating layer 61 in this order. The abrasive 71 and the weight 72 were rotated at 1800 rpm, and the load applied to the resin coating layer 61 was changed to measure the amount of decrease in the thickness of the resin coating layer 61. The amount of decrease in the thickness of the resin coating layer 61 was measured using an eddy current digital thickness gauge (“EDY-II” manufactured by Sanko Electronics Laboratory Co., Ltd.) that can detect a change in thickness of 0.1 μm.

  In the thrust wear test, the limit PV value was calculated. Here, the PV value is a product of the surface pressure (P) and the speed (V), and the limit PV value is a PV value at which the resin is melted by the frictional heat of the sliding surface and seized or abnormally worn. .

(Cross cut test)
The cross cut test was performed in order to evaluate the adhesive force between the substrate 60 and the resin coating layer 61. This cross cut test was carried out in accordance with JIS K 5400: 1998. Specifically, a 100 mm grid was prepared by penetrating a 1 mm square penetration through the resin coating layer 61 on the substrate 60, and an adhesive tape (“CT405AP-18” from Nichiban Co., Ltd.) was formed thereon. The operation of pasting and peeling was performed. The number of residual masses of the grids after the adhesive tape was applied and the peeling operation was set 500 times for each sample was examined.

  As is clear from Table 1, the resin coated bodies of Examples 1 to 5 have a higher pencil height than the resin coated bodies of Comparative Examples 3 and 4, and the thrust wear compared to the resin coated bodies of Comparative Examples 1 and 2 The abrasion amount of the resin coating layer in the test was small and the limit PV value was high, and the remaining number of grids in the grid test was large. Therefore, the resin coatings of Examples 1 to 5 were superior to the resin coatings of Comparative Examples 1 to 4 in the overall evaluation of the pencil hardness, the thrust wear test (including the limit PV value), and the cross cut test. Thus, from the results of Table 1, when the mass ratio of PTFE and PEEK in the mixed dispersion is in the range of 10:90 or more and 90:10 or less, the abrasion resistance of the resin coating layer obtained from the mixed dispersion is It can be said that it has excellent properties and adhesiveness.

<Examination of resin particle ratio less than 1 μm>
In the same manner as in Example 1, on the surface-treated aluminum alloy disk (base material), the mixed dispersion in which the resin particle ratio of less than 1 μm and the resin component ratio in the total resin particles are the values shown in Table 2 below. A resin coating layer was formed using the liquid. The film characteristics of this resin coating layer were evaluated as releasability, slidability and wear resistance. The evaluation results are shown in Table 2. The evaluation results in Table 2 are based on a single resin (PTFE 100% or PEEK 100%) in which the proportion of resin particles less than 1 μm is 0%, and show an improvement effect from this standard. It does not indicate an absolute evaluation of the characteristics related to the availability of the coating resin layer. Moreover, the notation of evaluation in Table 2 is as follows.

A: The improvement effect is remarkable compared with the reference single resin. B: The clear improvement effect is recognized compared with the reference single resin. C: The improvement effect is large compared with the reference single resin. D: There is no improvement effect compared to the standard single resin, or almost no (or standard)

(Releasability)
The releasability was evaluated as the adhesiveness of the adhesive tape to the resin coating. The lower the adhesiveness of this adhesive tape, the better the releasability.

(Sliding property)
The slidability was evaluated as a coefficient of dynamic friction with steel (S45C), 1,000 rpm, 16 MPa.

(Abrasion resistance)
The wear resistance was evaluated by visually observing the appearance of the resin coating layer when the load applied to the resin coating layer was increased in the thrust wear test, when the load was up to 15 MPa. This abrasion resistance evaluation was determined according to the following criteria.

  As is apparent from Table 2, when the mass ratio of PTFE to PEEK in the mixed dispersion is in the range of 10:90 or more and 90:10 or less, the ratio of the resin particles of less than 1 μm in the total resin particles is 20% or more and 100. When the ratio was less than or equal to%, good results were obtained in a comprehensive evaluation of releasability, slidability and wear resistance. Thus, from the results in Table 2, when the ratio of the resin particles of less than 1 μm in the mixed dispersion is adjusted to 20% or more and 100% or less, the releasability and sliding properties of the resin coating layer obtained from the mixed dispersion are determined. It can be seen that it has excellent mobility and wear resistance.

  ADVANTAGE OF THE INVENTION According to this invention, while enjoying the advantageous characteristics (for example, slidability, mold release property) which a fluororesin has, wear-resisting (mechanical strength) is improved, mixed resin molded object, and A mixed resin coating is provided. Therefore, the mixed resin coating and the mixed resin film of the present invention can be suitably used for sliding members such as bearings, actuator cylinders, piston members, and gear pumps.

DESCRIPTION OF SYMBOLS 1 Mixed resin coating 10, 20, 32 Base material 11, 21, 33 Resin coating layer 2 Winding bearing 3 Extrusion bearing 30 Cylindrical part 30A Outer surface 31 Flange part 34 Cylindrical part 35 Flange part 4, 4A Extrusion die 40 Die 41 point 42 space 43, 46 end face 44, 44A, 47, 47A resin coating layer 45 through hole 48, 48A flow path 49 resin outlet 5 covered electric wire 50 core conductor 51 outer skin 52 resin 6 resin coating 60 base material 61 resin coating Layer 70 Fixing member 71 Abrasive material 72 Weight

Claims (9)

A mixed resin composition in which resin particles are dispersed in a dispersion medium,
The resin particles include a perfluoropolymer and an aromatic polyether ketone,
The mass ratio of the perfluoropolymer to the aromatic polyether ketone is 10:90 or more and 90:10 or less,
A mixed resin composition in which the content of resin particles having a particle size of less than 1 μm among the resin particles is 20% by mass or more.   2. The mixed resin composition according to claim 1, wherein the resin particles are composed of first resin particles containing the perfluoropolymer as a main component and second resin particles containing the aromatic polyether ketone as a main component.   The mixed resin molding formed by irradiating an ionizing radiation to the coating film obtained by the coating and drying of the mixed resin composition of Claim 1 or Claim 2. Including a perfluoropolymer and an aromatic polyetherketone,
The mass ratio of the perfluoropolymer to the aromatic polyether ketone is 10:90 or more and 90:10 or less,
A mixed resin molded body in which chemical bonds are formed by irradiation with ionizing radiation.   The mixed resin molding according to claim 3 or 4, wherein the ionizing radiation is irradiated at a temperature equal to or higher than a melting point of the perfluoropolymer and the aromatic polyether ketone.   The mixed resin molded article according to claim 3, 4 or 5, which is in the form of a film. A substrate;
A mixed resin coating comprising: the mixed resin molded body according to any one of claims 3 to 6 formed on at least a part of an outer surface of the base material. A metal substrate;
A mixed resin coating comprising: the mixed resin molded body according to any one of claims 3 to 6 formed on at least a part of an outer surface of the metal base material.   The mixed resin coating according to claim 8, wherein at least an outer surface of the metal base material on which the mixed resin molded body is formed is roughened by etching.

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