JP2018059628A - Holder for rolling bearing and rolling bearing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a holder for a rolling bearing having a slide surface excellent in slidability even under a condition of oil lubrication, high slide speed and high plane pressure.SOLUTION: In order to hold a rolling body of a rolling bearing used under an oil lubrication environment, a holder for a rolling bearing comprises a cylindrical body having an outer diameter surface 5 and an end surface 7. The cylindrical body is composed of a base material and a slide layer formed on the surface of the base material. The slide layer is a fluorine resin film at least the surface of which is crosslinked. Push-in hardness of the slide layer on the outer diameter surface of the cylindrical body measured by the ISO 14577 method is made larger than push-in hardnesses of the slide layer on both end surfaces of the cylindrical body, and the push-in hardnesses of both end surfaces are substantially identical to each other.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a cage for a rolling bearing and a rolling bearing, and more particularly to a rolling bearing cage that has excellent wear resistance on the surface of the cage and can maintain the excellent wear resistance for a long period of time, and a rolling bearing using the cage. .

  Sliding surfaces such as rolling bearings and cages are supplied with lubricating oil or lubricating grease to reduce rolling friction or sliding friction. Further, a surface treatment for improving the slidability is applied to the sliding surface. One of the surface treatments is a method of forming a fluorine resin film. For example, a method for improving wear resistance and adhesion to a substrate by irradiating a polytetrafluoroethylene (hereinafter referred to as PTFE) coating formed on a sliding portion of a sliding member with a dose of 50 to 250 kGy. Is known (Patent Document 1).

  A fluororesin film is formed on the surface of a base material excellent in heat resistance selected from metal materials such as polyimide resin, copper, aluminum and alloys thereof, ceramics, and glass, and at a temperature equal to or higher than the melting point of the fluororesin. A method for producing a modified fluororesin coating material that emits ionizing radiation is known (Patent Document 2).

  As a sliding member made of fluororesin used for non-lubricated bearings, dynamic seals, etc., fluororesin is known in which fluororesin is heated above its crystalline melting point and irradiated with ionizing radiation in the absence of oxygen. (Patent Document 3).

  On the other hand, there are rolling bearings used for engines such as automobiles and motorcycles, in particular needle roller bearings with a cage, and the surface of the cage is silver-plated to prevent seizure of the surface of the cage. This needle roller bearing with a cage is composed of a pressed metal cage that holds the needle rollers at regular intervals, and the entire surface of the cage is silver-plated (Patent Document 4).

JP 2010-155443 A JP 2002-225204 A JP-A-9-278907 Japanese Patent No. 5189427

However, the manufacturing method shown in Patent Document 1 is a method for improving adhesion to a substrate because it is used under non-lubricated conditions under low surface pressure, and is required for the sliding surface of a rolling bearing cage. It is difficult to apply in the case of high lubricating speed, high sliding speed and high surface pressure.
The fluororesin coating described in Patent Document 2 is intended to simultaneously cause a cross-linking reaction of a fluororesin and a chemical reaction between the fluororesin and a substrate surface, thereby achieving strong adhesion between the two. In the case of an iron substrate such as a cage or a cage, it is difficult to generate a chemical reaction with the surface of the substrate, and there is a problem that strong adhesion cannot be achieved.
The sliding member described in Patent Document 3 is used for a non-lubricated bearing, a dynamic seal, and the like, and relates to a sliding member made of a fluororesin rather than a film shape. Therefore, the characteristics as a coating material are unclear, and it is difficult to apply to rolling bearing cages that require high slip speed and high surface pressure in lubricating oil.
In the cage to which silver plating described in Patent Document 4 is applied, a cage with less change with time in the wear amount of the sliding surface is required, and a sliding material in place of silver plating is required. . Further, silver plating has a problem that it is sulfided by a sulfur component contained in engine oil. When the silver plating applied to the surface of the cage is sulfided, peeling or dropping occurs from the cage, and the base material of the cage is exposed.

  The present invention has been made to cope with such a problem, and is a rolling bearing holding having a sliding surface excellent in slidability even under conditions of high sliding speed and high surface pressure in lubricating oil. It is an object of the present invention to provide a rolling bearing using the cage and the cage.

  The rolling bearing retainer of the present invention comprises a cylindrical body having an outer diameter surface and an end surface adjacent to the outer diameter surface in order to hold the rolling element of the rolling bearing used in an oil lubricated environment. The cylindrical body includes a base material and a sliding layer formed on the surface of the base material. This sliding layer is a fluororesin film having at least a surface crosslinked, and the indentation hardness of the sliding layer on the outer diameter surface of the cylindrical body measured by the ISO14577 method is the indentation of the sliding layer on the end surface of the cylindrical body. It is characterized by being larger than the hardness. In particular, the indentation hardness of the sliding layer on the outer diameter surface of the cylindrical body is 58 to 140 MPa, and the indentation hardness of the sliding layer on the end surface of the cylindrical body is 55 to 109 MPa. Further, the indentation hardness of the sliding layer on the left and right end faces of the cylindrical body is substantially the same.

In the rolling bearing cage of the present invention, the sliding layer includes a base layer containing a heat-resistant resin and a first fluororesin formed on the surface of the base material, and a second layer formed on the surface of the base layer. It consists of a fluororesin layer, and at least the surface of the second fluororesin layer is crosslinked.
Moreover, the layer thickness of the said sliding layer in the cage for rolling bearings of this invention is 10 micrometers or more and less than 40 micrometers, It is characterized by the above-mentioned. The base material is an iron-based metal material.

  The rolling bearing of the present invention is a rolling bearing attached to an end of a connecting rod that supports a crankshaft that outputs rotational motion and converts linear reciprocating motion into rotational motion, or attached to the crankshaft. The cage that holds the rolling elements of the rolling bearing is the cage of the present invention.

  In the rolling bearing cage of the present invention, the indentation hardness of the sliding layer on the outer diameter surface of the cage cylinder is larger than the indentation hardness of the sliding layer on both end surfaces of the cylinder. Since the indentation hardness of the sliding layer on both end faces is substantially the same, wear can be suppressed and the life of the bearing can be maintained for a long time even under conditions of high slip speed and high surface pressure in the lubricating oil. The ferrous metal material cage having this sliding layer exhibits a sliding property equal to or higher than that of a cage having a silver plating layer. Moreover, the rolling bearing using this cage is excellent in slidability in lubricating oil as a connecting rod rolling bearing used in lubricating oil.

It is a perspective view of the cage for needle bearings. It is a figure which shows an electron beam irradiation apparatus. It is an enlarged view of the NMR chart at the time of PTFE resin non-irradiation. It is an enlarged view of the NMR chart at the time of 500 kGy irradiation. It is an enlarged view of the NMR chart at the time of 1000 kGy irradiation. It is a graph of the signal intensity | strength which intensity | strength increases with bridge | crosslinking. It is a perspective view which shows a needle roller bearing. It is a longitudinal cross-sectional view of a 4-cycle engine. It is a figure which shows the outline | summary of an abrasion amount test apparatus. It is a figure which shows the apparatus used for the electron beam irradiation of the comparative example 8.

An example of a rolling bearing cage is shown in FIG. FIG. 1 is a perspective view of a needle bearing retainer. As shown in FIG. 1, the needle bearing retainer 1 includes a plurality of pocket portions 2 that hold rolling elements, a column portion 3 that is positioned between the pocket portions 2 and that extends along the axial direction, and a column portion 3. And a cylindrical portion 4 fixed on both sides in the axial direction. The column portion 3 and the cylindrical portion 4 have an outer diameter surface 5 and an inner diameter surface 6, and the cylindrical portion 4 has an end surface 7 composed of two end surfaces 7 a and 7 b adjacent to the outer diameter surface 5 and the inner diameter surface 6, respectively. ing.
The rolling bearing cage of the present invention is not limited to a needle bearing cage, but also includes a ball bearing cage having a circular pocket portion.

As a material of the rolling bearing cage, an iron-based metal material is preferable.
Examples of the iron-based metal material include bearing steel used for rolling bearings, carburized steel, carbon steel for machine structure, cold rolled steel, hot rolled steel, and the like. The iron-based metal material is adjusted to a predetermined surface hardness by quenching and tempering after processing into the shape of the sliding member. For example, in the case of a ferrous metal material cage using chromium molybdenum steel (SCM415), it is preferable to use an ferrous metal material whose Hv value is adjusted to 484 to 595.

  A cage 1 having a plurality of pocket portions 2 for holding rolling elements is a method in which a cylinder is cut out from a shaped material, and the pocket portions 2 are formed by stamping by pressing. After pressing a flat plate, an appropriate length is obtained. It can manufacture by the method etc. which are cut | judged, rounded into a cylindrical shape, and joined by welding.

  The cage 1 has a sliding layer formed on the surface thereof. This sliding layer is a fluororesin film having at least a surface crosslinked. When the indentation hardness of the sliding layer on the outer diameter surface 5 is Ho, the indentation hardness of the sliding layer on the end surface 7a is He, and the indentation hardness of the sliding layer on the end surface 7b is He ', Ho> He And Ho> He ′, and He and He ′ are substantially the same. Here, the indentation hardness is measured by the ISO14577 method. More specifically, the indentation hardness of the sliding layer on the outer diameter surface of the cylinder is 58 to 140 MPa while the indentation hardness is satisfied, and the indentation hardness of the sliding layer on the end surface of the cylinder is 55. It is preferable that it is -109MPa.

  The fluororesin film having at least a surface crosslinked preferably comprises a base layer formed on the surface of the iron-based metal material and a cross-linked fluororesin layer formed on the surface of the base layer. The underlayer is a mixture layer containing a heat-resistant resin and a fluororesin that can be mixed with the heat-resistant resin (hereinafter referred to as a first fluororesin). Improves adhesion.

The heat resistant resin is a resin that is not thermally decomposed in the firing step when forming the base layer and the upper layer film. Here, “not thermally decomposed” means a resin that does not start thermal decomposition within the temperature and time for firing the underlayer and the upper layer film. The heat-resistant resin is preferably a resin having a functional group excellent in adhesion to the iron-based metal material and a functional group that reacts with the first fluororesin in the molecular main chain or at the molecular end.
Examples of the heat resistant resin include epoxy resin, polyester resin, polyamideimide resin, polyimide resin, polyetherimide resin, polyimidazole resin, polyethersulfone resin, polysulfone resin, polyetheretherketone resin, and silicone resin. Moreover, the urethane resin and acrylic resin which prevent the shrinkage | contraction at the time of fluororesin formation of a coating film can be used together.

  The first fluororesin can be used as long as it is a resin that can be dispersed in the form of particles in the aqueous coating liquid that forms the base layer. As the first fluororesin, PTFE particles, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as PFA) particles, tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP) particles, Or these 2 or more types can be used preferably.

  In addition to the heat-resistant resin and the first fluororesin, the aqueous coating solution for forming the underlayer includes a nonionic surfactant such as polyoxyethylene alkyl ether, an inorganic pigment such as carbon black, N-methyl-2-pyrrolidone An aprotic polar solvent that is arbitrarily mixed with water, such as water, and water as a main solvent are blended. Moreover, an antifoamer, a desiccant, a thickener, a leveling agent, a repellency inhibitor, etc. can be mix | blended. Examples of the aqueous coating solution for forming the undercoat layer include primer paints EK series and ED series manufactured by Daikin Industries, Ltd.

  The fluororesin (hereinafter referred to as second fluororesin) layer on the surface forming the sliding layer is a fluororesin layer that is formed on the surface of the underlayer and can be cross-linked by radiation. The first fluororesin and the second fluororesin may be the same or different, but it is preferable to use the same fluororesin. Examples of the second fluororesin include PTFE, PFA, FEP, ethylene / tetrafluoroethylene copolymer (ETFE), and the like. These resins can be used alone or as a mixture. Among these, PTFE is preferable because it undergoes a crosslinking reaction by irradiating with an electron beam near the melting point, and is excellent in heat resistance and slidability.

  The second fluororesin layer is obtained by applying and drying an aqueous dispersion in which PTFE resin particles are dispersed. Examples of the aqueous dispersion in which PTFE resin particles are dispersed include, for example, Polyflon = PTFE enamel manufactured by Daikin Industries, Ltd.

A method for forming the sliding layer on the surface of the iron-based metal material will be described below.
(1) Surface treatment of iron-based metal material For iron-based metal material, the roughness (Ra) of the metal material surface is adjusted to 1.0 to 2.0 μm in advance using shot blasting before forming the sliding layer. Thereafter, it is preferably immersed in an organic solvent such as air blow or petroleum benzine and subjected to ultrasonic cleaning for about 5 minutes to 1 hour.
(2) Application of aqueous coating solution for forming the underlayer Before applying the aqueous coating solution for forming the underlayer, in order to improve the dispersibility of the aqueous dispersion, use a ball mill, for example, to rotate at 40 rpm for 1 hour. Redistribute. This re-dispersed aqueous coating solution is filtered using a 100 mesh wire netting and applied using a spray method.
(3) Drying the aqueous coating solution for forming the undercoat layer After coating the aqueous coating solution, it is dried. As drying conditions, for example, drying in a thermostat at 90 ° C. for about 30 minutes is preferable. The layer thickness of the base layer after drying is 5 μm or more and less than 20 μm, preferably 10 to 15 μm. If the thickness is less than 5 μm, the metal substrate may be exposed due to peeling due to poor adhesion of the coating or wear due to initial wear. If the thickness is 20 μm or more, cracks during film formation or peeling during operation may deteriorate the lubrication state. By setting the layer thickness in the range of 5 μm or more and less than 20 μm, it is possible to prevent the metal substrate from being exposed due to initial wear, and to prevent peeling during operation over a long period of time.

(4) Application of aqueous coating liquid for forming the second fluororesin layer Before the aqueous coating liquid for forming the second fluororesin layer, in order to improve the dispersibility of the aqueous dispersion, using a ball mill, for example, Rotate at 40 rpm for 1 hour to redisperse. The re-dispersed aqueous coating solution is filtered using a 100 mesh wire net and painted using a spray method.
(5) Drying of the aqueous coating solution for forming the second fluororesin layer The aqueous coating solution is applied and then dried. As drying conditions, for example, drying in a thermostat at 90 ° C. for about 30 minutes is preferable. The layer thickness of the second fluororesin layer after drying is 5 μm or more and less than 20 μm, preferably 10 to 15 μm. If the thickness is less than 5 μm, the metal substrate may be exposed due to peeling due to poor adhesion of the coating or wear due to initial wear. If the thickness is 20 μm or more, cracks during film formation or peeling during operation may deteriorate the lubrication state. By setting the layer thickness in the range of 5 μm or more and less than 20 μm, it is possible to prevent the metal substrate from being exposed due to initial wear, and to prevent peeling during operation over a long period of time.
In addition, as a coating method of a base layer and a 2nd fluororesin layer, what can form a film, such as a dipping method and a brush coating method other than a spray method, can be used. The spray method is preferable in view of making the surface roughness and coating shape of the coating as small as possible and considering the uniformity of the layer thickness.

(6) Firing After drying the second fluororesin layer, in the heating furnace, in the air, a temperature equal to or higher than the melting point of the second fluororesin, preferably (melting point (Tm) + 30 ° C.) to (melting point (Tm) + 100 ° C. ) And firing within a range of 5 to 40 minutes. When the first and second fluororesins are PTFE, they are preferably fired in a heating furnace at 380 ° C. for 30 minutes.

(7) Hardening of the second fluororesin layer In the film after firing, the irradiation temperature is 30 ° C lower than the melting point of the second fluororesin layer to 20 ° C or less higher than the melting point, and the outside of the cage Radiation so that the indentation hardness Ho of the radial surface coating and the indentation hardness He and He ′ of the coating on both ends of the cage are larger than the indentation hardness of the unirradiated fluororesin (however, Ho> He and Ho> He ′). To increase the hardness of the fluororesin layer. Radiation irradiation crosslinks the fluororesin and increases the surface hardness. Radiation includes α rays (particle beams of helium-4 nuclei emitted from radionuclides that undergo α decay), β rays (negative electrons and positrons emitted from nuclei), electron beams (almost constant kinetic energy). Particle beam such as electron beam, generally generated by accelerating thermionic electrons in vacuum; gamma ray (emitted and absorbed by transitions between energy levels of nuclei and elementary particles, pair annihilation of elementary particles, pair production, etc.) Ionizing radiation such as an electromagnetic wave having a short wavelength). Among these radiations, from the viewpoint of crosslinking efficiency and operability, electron beams and γ rays are preferable, and electron beams are more preferable. In particular, an electron beam has advantages such as easy availability of an electron beam irradiation apparatus, simple irradiation operation, and the ability to employ a continuous irradiation process. Similar effects can be obtained by plasma irradiation or addition of a radical generator in addition to radiation irradiation.

  The hardness of the fluororesin layer does not sufficiently increase except in the temperature range where the irradiation temperature is 30 ° C. lower than the melting point of the second fluororesin layer to 20 ° C. higher than the melting point. Also, in order to efficiently increase the hardness of the coating applied to the outer diameter surface and the end surface, it is necessary to lower the oxygen concentration in the irradiated region by injecting inert gas. The range of oxygen concentration is preferably 0 to 300 ppm. In order to maintain the oxygen concentration in the above concentration range, an inert atmosphere by nitrogen gas injection is preferable from the viewpoint of operability and cost.

A method for electron beam irradiation will be described with reference to FIG. 2 so that the indentation hardness of the surface of the sliding layer has a relationship of Ho> He and Ho> He ′, and He and He ′ are substantially the same. . FIG. 2 is a diagram showing an electron beam irradiation apparatus, FIG. 2 (a) is a schematic front view, FIG. 2 (b) is a diagram showing a diametrical cross section of a cage fixing jig, and FIG. ) Is a diagram showing a film dosimeter pasting location.
In the electron beam irradiation chamber 8, a plurality of cages 1 are coaxially arranged on the outer periphery of the cage fixing jig 9, and the electron beam is removed from the electron beam irradiation window 8a while rotating around the cylindrical axis of the cage 1. Irradiation is performed in a direction perpendicular to the radial surface 5. The cage 1 is rotated by rotational power obtained from a motor 11 connected to a rotation shaft 10 of a cylindrical cage fixing jig 9 that is fitted to the inner diameter surface of the cage 1. The cage fixing jig 9 is fitted to the inner diameter portion of the cage 1 to such an extent that the cage does not idle, and the rotating shaft 10 of the cage fixing jig 9 is arranged in a direction perpendicular to the electron beam irradiation direction. Is a fixture. Reference numeral 10a denotes a connecting portion of the rotating shaft.

  Inside the cage fixing jig 9, a heating source 12 such as a cartridge heater and a control device 13 such as a heater control thermocouple are provided. The heating source 12 and the control device 13 are connected to an external power source and a temperature control device via a rotary connector 14. The linear expansion coefficient of the cage fixing jig 9 is preferably larger than the linear expansion coefficient of the material of the cage 1. By setting the linear expansion coefficients of the cage fixing jig 9 and the cage 1 within the above range, the cage 1 can be fixed and efficiently heated when the electron beam is irradiated while heating.

  The material of the cage fixing jig 9 varies depending on the material, size, shape, etc. of the cage 1, but when the material of the cage 1 is steel, it does not change due to linear expansion coefficient, thermal conductivity, or electron beam irradiation. From the viewpoint of substances, aluminum is preferable, and from the viewpoint of economy, 1000 series aluminum which is pure aluminum having a purity of 99.00% or more is more preferable.

  The inside 8b of the electron beam irradiation chamber 8 is filled with nitrogen. By irradiating the electron beam in a nitrogen atmosphere, the electron beam is also irradiated in the direction of the two end surfaces 7 a and 7 b of the cage 1 along with the outer diameter surface 5 of the cage 1. As a preferable nitrogen atmosphere, nitrogen convection may be mentioned so that the oxygen concentration is 300 ppm or less in the chamber. Moreover, 60-70 rpm is mentioned as a rotation speed of a preferable rotating shaft.

The irradiation dose to the outer diameter surface of the cage is preferably 230-2400 kGy. The surface hardness of the sliding layer can be adjusted within this irradiation dose range.
The acceleration voltage for electron beam irradiation is preferably 10 to 300 kV, more preferably 10 to 100 kV. The present invention can irradiate the two end faces 7a and 7b together with the outer diameter surface 5 of the cage 1 even when the acceleration voltage is low energy electron beam irradiation of several tens of kV. The electron beam irradiation is direct irradiation in which the electron beam vertically enters the outer diameter surface 5, and the end surfaces 7a and 7b are irradiated by scattering of the electron beam. Therefore, the electron beam irradiation is outside the both end surfaces 7a and 7b of the cage. The radial surface 5 has a higher irradiation dose. As a result, since the energy application rate of the electron beam is high with respect to the outer diameter surface resin layer that requires the most sliding characteristics in the rolling bearing cage, the irradiation method is suitable for the rolling bearing cage. As a result of irradiation, by irradiating the outer diameter surface 5 and the end surfaces 7a and 7b, the wear amount of the outer diameter surface 5 can be increased, the exposure of the metal base material can be prevented, and the coating on the end surface and the balance weight or Even when sliding with the side washer, the coating does not disappear due to wear.

Next, it will be described that the second fluororesin layer on the surface of the rolling bearing cage of the present invention has a crosslinked structure. In general, a fluorine-based resin, particularly a PTFE resin, is chemically very stable and extremely stable against an organic solvent, so that it is difficult to identify the molecular structure or molecular weight. Furthermore, since the cage surface of the present invention forms a three-dimensional structure by cross-linking, it becomes more difficult to dissolve in a solvent, and structural analysis becomes more difficult. However, measurement and analysis by ¹⁹ F Magical Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) Method (High Speed Magical Nuclear Magnetic Resonance) makes it possible to identify the three-dimensional structure of the cage surface of the present invention. .

The measurement is performed using an NMR device JNM-ECX400 manufactured by JEOL Ltd., and a suitable measurement nuclide ( ¹⁹ F), resonance frequency (376.2 MHz), MAS (Magic Angle Spinning) rotation speed (15 and 12 kHz), sample amount (About 70 μL in a 4 mm solid state NMR tube), a cycle time (10 seconds) and a measurement temperature (about 24 ° C.). The results are shown in FIGS. FIG. 3 shows NMR when PTFE resin is not irradiated, FIG. 4 shows NMR when PTFE resin is irradiated with 500 kGy, and FIG. 5 shows an enlarged view of an NMR chart when PTFE resin is irradiated with 1000 kGy. 3 to 5, the upper stage represents the MAS rotational speed 15 kHz, and the lower stage represents the MAS rotational speed 12 kHz. FIG. 6 is a graph obtained by normalizing the signal intensity at −82 ppm, the intensity of which increases with crosslinking, with the signal intensity at −122 ppm as the main signal. In FIG. 6, the upper part represents the measured value, and the lower part represents the graph. It is considered that the higher the signal intensity ratio is, the more the degree of crosslinking proceeds.

When the second fluororesin layer (0 kGy) not irradiated with radiation is measured under the above conditions, signals of -82 ppm, -122 ppm, and -162 ppm, which are chemical shift values (δ ppm), are observed at a MAS speed of 15 kHz. (The upper part of FIG. 3). Similarly, signals of −58 ppm, −82 ppm, −90 ppm, −122 ppm, −154 ppm, and −186 ppm were observed at the MAS rotational speed of 12 kHz (lower part of FIG. 3). It is known that −122 ppm is the signal of the F atom in the —CF ₂ —CF ₂ — bond, and −82 ppm is the signal of the F atom of —CF ₃ in the —CF ₂ —CF ₃ bond. From this, the signals of −82 ppm and −162 ppm at a MAS rotational speed of 15 kHz and −58 ppm, −90 ppm, −154 ppm, and −186 ppm at a MAS rotational speed of 12 kHz are spinning side bands (SSB). In addition, in the range of −122 ppm to −130 ppm, a broad signal is observed hidden behind the −122 ppm signal. This signal is a signal of the F atom of —CF ₂ — in the —CF ₂ —CF ₃ bond that should be observed at −126 ppm. Therefore, PTFE resin layer of uncrosslinked not performed Irradiation -CF ₂ -CF ₂ - -122ppm attributable to binding, by NMR chart having a signal of -82ppm and -126ppm attributable to -CF ₂ -CF ₃ expressed.

When the solid ¹⁹ F MAS NMR of the second fluororesin layer (500 kGy) irradiated with a dose of 500 kGy was measured under the same conditions as the uncrosslinked second fluororesin layer, −68 ppm, except for the spinning sideband, Signals of −70 ppm, −80 ppm, −82 ppm, −109 ppm, −112 ppm, −122 ppm, −126 ppm, −152 ppm, and −186 ppm were observed (FIG. 4 top) and FIG. 4 bottom). Signals of −68 ppm, −70 ppm, −80 ppm, −109 ppm, −112 ppm, −152 ppm, and −186 ppm newly appeared by irradiation, and the signal intensity of the −82 ppm signal increased from that of unirradiated.

When solid ¹⁹ F MAS NMR of the second fluororesin layer (1000 kGy) irradiated with a dose of 1000 kGy was measured under the same conditions as the uncrosslinked PTFE resin, −68 ppm, −70 ppm, −− Signals of 77 ppm, -80 ppm, -82 ppm, -109 ppm, -112 ppm, -122 ppm, -126 ppm, -152 ppm, and -186 ppm were observed (the upper part of FIG. 5 and the lower part of FIG. 5). -68 ppm, -70 ppm, -77 ppm, -80 ppm, -109 ppm, -112 ppm, -152 ppm, and -186 ppm signals newly appear by irradiation, and the signal intensity of -82 ppm is higher than that at 500 kGy irradiation. It was.

The above signal can be expressed by underlining the assigned F atom. For example, -70 ppm is = CF-C F ₃ , -109 ppm is -C F ₂ -CF (CF ₃ ) -C F _2- , -152 ppm is = C F -C F =, -186 ppm is known to be attributed to ≡C F (Beate Fuchs and Ulrich Scheler., Branching and Cross-Linking in Radiation-Modified Poly (tetrafluorethylene) Int. Macromolecules, 33, 120-124.2000).

These signals indicate the presence of chemically non-equivalent fluorine atoms and at the same time indicate that the PTFE resin layer forms a three-dimensional structure due to crosslinking. Further, according to the above document, the signal intensity of the observed signal is stronger at the irradiation dose of 1000 kGy than the irradiation dose of 500 kGy, and the signal intensity of the signal increases as the irradiation dose increases at least up to the irradiation dose of 3000 kGy. It is known to be. In addition, about the signal which is not described in the said literature, although it is possible that the structure of a fluororesin layer differs with the difference in the irradiation conditions of a radiation, it is = CF-C F that a crosslinked structure is formed. It is obvious from the existence of structures such as ₃ , —C F ₂ —CF (CF ₃ ) —C F ₂ —, ═C F —C F ═, ≡C F.

  As shown in FIG. 6, the normalized signal intensity ratio increases as the irradiation dose increases. When the irradiation dose was 500 kGy, a clearly crosslinked structure appeared, and when the irradiation dose was doubled to 1000 kGy, the normalized signal intensity ratio was about three times, indicating that the crosslinking was more advanced.

  The layer thickness of the sliding layer obtained by the method described above is 10 μm or more and less than 40 μm, preferably 15 μm or more and less than 30 μm. If the layer thickness is less than 10 μm, the metal substrate may be exposed due to peeling due to poor adhesion of the coating or wear due to initial wear. If it is 40 μm or more, cracks during film formation or peeling during operation may deteriorate the lubrication state. By setting the layer thickness to a range of 10 μm or more and less than 40 μm, it is possible to prevent the metal substrate from being exposed due to initial wear and to prevent peeling during operation over a long period of time.

  The rolling bearing cage of the present invention has a sliding layer with excellent adhesion to an iron-based metal material and a sliding surface with excellent wear resistance even in oil. Suitable for bearings. It is particularly suitable for a connecting rod large end bearing, a connecting rod small end bearing, or a crankshaft support shaft, which is a rolling bearing that uses needle rollers as rolling elements and is used in oil.

  FIG. 7 is a perspective view showing a needle roller bearing which is an embodiment of a rolling bearing. As shown in FIG. 7, the needle roller bearing 15 includes a plurality of needle rollers 16 and a cage 1 that holds the needle rollers 16 at regular intervals or unequal intervals. In the case of an engine connecting rod part bearing, no bearing inner ring and bearing outer ring are provided, and a shaft such as a crankshaft or a piston pin is directly inserted into the inner diameter side of the cage 1, and the outer diameter side of the cage 1 is a housing. It is used by being fitted into the engagement hole of a certain connecting rod. Since the needle roller 16 having no inner and outer rings and having a smaller diameter than the length is used as a rolling element, the needle roller bearing 15 is more compact than a general rolling bearing having inner and outer rings. Become.

FIG. 8 shows a longitudinal sectional view of a four-cycle engine using the needle roller bearing.
FIG. 8 is a longitudinal sectional view of a four-cycle engine using a needle roller bearing as an example of the rolling bearing of the present invention. In the four-cycle engine, the intake valve 17a is opened, the exhaust valve 18a is closed, and an air-fuel mixture obtained by mixing gasoline and air is sucked into the combustion chamber 19 through the intake pipe 17, and the intake valve 17a is closed and the piston 20 is closed. And a compression stroke in which the air-fuel mixture is compressed, an explosion stroke in which the compressed air-fuel mixture is exploded, and an exhaust stroke in which the exploded combustion gas is exhausted through the exhaust pipe 18 by opening the exhaust valve 18a. The piston 20 that performs linear reciprocating motion by combustion in these strokes, the crankshaft 21 that outputs rotational motion, the connecting rod 22 that connects the piston 20 and the crankshaft 21 and converts linear reciprocating motion into rotational motion, Have The crankshaft 21 rotates about a rotation center shaft 23 and balances rotation by a balance weight 24.

The connecting rod 22 is formed by providing a large end 25 below the linear rod and a small end 26 above. The crankshaft 21 is rotatably supported via a needle roller bearing 15 a attached to the engagement hole of the large end portion 25 of the connecting rod 22. If necessary, a steel or copper alloy side washer is disposed between the balance weight, the connecting rod large end side surface, and the bearing end surface. The piston pin 27 that connects the piston 20 and the connecting rod 22 is rotatably supported via a needle roller bearing 15b attached to the engagement hole of the small end portion 26 of the connecting rod 22.
By using a needle roller bearing with excellent slidability, even a two-cycle engine or a four-cycle engine reduced in size or increased in output has excellent durability.

  Although FIG. 7 illustrates a needle roller bearing as the bearing, the rolling bearing of the present invention is a cylindrical roller bearing, a tapered roller bearing, a self-aligning roller bearing, a needle roller bearing, a thrust cylindrical roller bearing, or a thrust cone other than those described above. It can also be used as a roller bearing, a thrust needle roller bearing, a thrust self-aligning roller bearing or the like. In particular, it can be suitably used for a rolling bearing that is used in an oil-lubricated environment and uses a ferrous metal material cage.

Examples 1 to 5
A needle bearing retainer (base surface hardness Hv: 484 to 595) made of chromium molybdenum steel (SCM415) subjected to carburizing, quenching and tempering and having an outer diameter of φ44 mm, an inner diameter of φ37 mm, and a width of 22 mm was prepared. Each surface is roughened to a surface roughness Ra of about 1 μm by blasting and washed, and then the primer layer is a Daikin primer paint (model number: EK-1909S21R), and the second fluororesin layer is a Daikin top paint ( The sliding layer was formed using model number: EK-3700C21R). The drying time was 30 minutes in a constant temperature bath at 90 ° C., followed by baking in a heating furnace at 380 ° C. for 30 minutes. Then, the electron beam was irradiated by the method shown in FIG. 2 so that the indentation hardness of the surface of a sliding layer might become predetermined | prescribed hardness shown in Table 3.

  The cage 1 having a non-irradiated sliding layer on the surface thereof is inserted into an aluminum cage fixing jig 9 into which a cartridge heater as a heating source 12 is inserted. The cage fixing jig 9 was connected to a motor 11 and irradiated an electron beam to the entire coating by passing through an electron beam generation source while rotating at a rotational speed of 60 to 70 times / minute during electron beam irradiation. That is, in FIG. 2, the electron beam was irradiated from the upper part of the drawing, and the cage fixing jig 9 was slid toward the front of the drawing. Further, the temperature of the cage was preset in the range from a temperature 30 ° C. lower than the melting point of the coating to 20 ° C. higher than the melting point by the cartridge heater as the heating source 12. The irradiation dose to the outer diameter surface of the cage was 236 kGy in Example 1, 944 kGy in Example 2, 1652 kGy in Example 3, and 2360 kGy in Example 4 and Example 5. In order to efficiently increase the hardness of the coating applied to the outer diameter surface and the end surface, the irradiation atmosphere was filled with nitrogen so that the oxygen concentration in the irradiation region was 300 ppm or less by injecting inert gas. .

  The hardness of the coating was measured by replacing it with a flat test piece because measurement using a cage such as fixing of the sample becomes complicated. At that time, in order to grasp the irradiation dose of the electron beam to the cage, 7 locations (FIG. 2 (c)) of 5a to 5g on the outer diameter surface and 2 locations of 7a and 7b (FIG. 2 (a)) on both end surfaces. ), The electron beam was irradiated to the holder in which film dosimeters (radiochromic film “FWT-60-810” manufactured by FWT) were attached to a total of nine places. When a film dosimeter is attached, the cage is not heated. Using the film dosimeter after electron beam irradiation, the irradiation dose was measured with a dosimeter (FWT-92D type radiochromic film reader). The results are shown in Table 1.

表１に示すように、外径面（５ａ〜５ｇ）に照射された照射線量の平均値を算出すると２８．２９ｋＧｙであり、端面（７ａおよび７ｂ）の平均値は１８．６５ｋＧｙであるので、電子線の６５．９％が端面に照射されることがわかった。したがって、外径面に２３６０ｋＧｙ照射すると端面には１５５５ｋＧｙ照射される。この結果を踏まえて、ＳＰＣＣ製３０ｍｍ×３０ｍｍ×厚さ２ｍｍの平板に実施例１〜実施例５と同様の条件で表面フッ素樹脂被膜を形成し、実施例１〜実施例５と同様の条件およびその６５．９％の線量となる電子線を照射して、平板試験片（外径面相当、端面相当）とした。同様にＳＣＭ４１５製３ｍｍ×３ｍｍ×２０ｍｍの角棒を３本ずつ（合計表面積７７４ｍｍ²）準備して、実施例１〜実施例５と同様に被膜形成および電子線照射して、潤滑油浸漬試験片とした。

As shown in Table 1, when the average value of the irradiation dose irradiated on the outer diameter surface (5a to 5g) is calculated, it is 28.29 kGy, and the average value of the end surfaces (7a and 7b) is 18.65 kGy. It was found that 65.9% of the electron beam was applied to the end face. Therefore, when the outer diameter surface is irradiated with 2360 kGy, the end surface is irradiated with 1555 kGy. Based on this result, a surface fluororesin film was formed on a flat plate of 30 mm × 30 mm × 2 mm thickness made of SPCC under the same conditions as in Examples 1 to 5, and the same conditions as in Examples 1 to 5 and An electron beam having a dose of 65.9% was irradiated to form a flat plate test piece (corresponding to an outer diameter surface and an end surface). Similarly, three 3 mm × 3 mm × 20 mm square bars made of SCM415 (total surface area of 774 mm ² ) were prepared, and film formation and electron beam irradiation were performed in the same manner as in Example 1 to Example 5 to obtain a lubricating oil immersion test piece. It was.

The obtained flat plate test piece, needle bearing cage and lubricating oil immersion test piece were evaluated by the following methods.
[Indentation hardness]
Agilent Technologies, Inc .: Using a nanoindenter (G200), measurement was performed using a flat plate test piece by a method based on ISO14577. In addition, the measured value has shown the average value of the depth (location where hardness is stable) which is not influenced by surface roughness and a base material (SPCC), and measured 10 each test piece. The measurement conditions are such that the indenter shape is a Barkovic type, the indentation depth is a depth at which the load is 5 mN, the load load speed is 10 mN / min, and the measurement temperature is 25 ° C. The indentation hardness was calculated from the indentation load and displacement (area). The results are shown in Table 3. The indentation hardness shown in Table 3 is obtained by using the sample in which the main plane of the flat plate test piece is arranged in the direction perpendicular to the irradiation direction of the electron beam, and the indentation hardness of the outer diameter surface equivalent test piece The indentation hardness and the indentation hardness of the end surface equivalent test piece were measured as end surface indentation hardness, respectively.

[Abrasion amount and peeling amount]
An outline of the wear amount test apparatus is shown in FIG.
Rotating in a state in which a concave mating material 28 made of SUJ2 and quenched and tempered HRC62 and having a concave surface roughness of 0.1 to 0.2 μmRa is pressed from the vertical direction to the cage 1 attached to the rotary shaft with a predetermined load 29. The friction characteristics of the coating applied to the surface of the cage 1 were evaluated by rotating the cage 1 together with the shaft, and the amount of wear was measured. The measurement conditions are load: 440N, lubricating oil: mineral oil (10W-30), sliding speed: 930.6 m / min, measurement time: 100 hours. Moreover, the adhesiveness of the PTFE coating was also evaluated by visually observing the amount of peeling at that time. The amount of peeling is heavy when the metal substrate is exposed, and the light amount is when the metal substrate is not exposed. The radius of the concave R portion was set to a size 20 to 55 μm larger than the cage radius. Lubricating oil was used in an amount soaking up to half the height of the cage. The results are shown in Table 3.

[Elution volume]
150 g of lubricating oil immersion test piece (poly-α-olefin: Lucant HL-10 (manufactured by Mitsui Chemicals) added with 1% by weight of ZnDTP (LUBRIZOL677A, manufactured by LUBRIZOL)) 2.2 g After being soaked for 200 hours, the concentration of the coating component eluted in the lubricating oil (unit of elution amount, ppm) was measured. The concentration was quantified by fluorescent X-ray measurement [fluorescent X-ray measurement apparatus: Rigaku ZSX100e (manufactured by Rigaku Corporation)]. The results are shown in Table 3.

Comparative Example 1
Except not irradiating an electron beam, the same evaluation as Example 1 was performed using the same sample as Example 1. The results are shown in Table 3.

Comparative Examples 2-3
The same evaluation as in Example 1 was performed using the same sample as in Example 1 except that the electron beam irradiation dose was made lower than that in Example 1 and the indentation hardness was made lower than in Example 1. The results are shown in Table 3.

Comparative Examples 4-5
The same evaluation as in Example 1 was performed using the same sample as in Example 1 except that the electron beam irradiation dose was increased from that in Example 4 and the indentation hardness was made higher than in Example 4. The results are shown in Table 3.

Comparative Example 6
Except that the thickness of the sliding layer was 40 μm, the sliding layer was formed using the same sample as in Example 1. However, since cracks occurred during the firing stage of the sliding coating, Canceled.

Comparative Example 7
Using the same metal substrate as in Example 1, the second fluororesin layer was directly formed with the same coating solution and conditions as in each Example without forming the underlayer, and the same indentation as in Example 2 It was irradiated with an electron beam so as to be hard. Table 3 shows the results of the same evaluation as in Example 1.

Comparative Example 8
The same unirradiated sliding film as in Example 1 was formed and irradiated with an electron beam using the irradiation apparatus shown in FIG. FIG. 10 is a view showing an electron beam irradiation apparatus in Comparative Example 8, FIG. 10 (a) is a schematic front view, and FIG. 10 (b) is a view showing a film dosimeter pasting position.
The cage 1 'is placed on the installation table 30 so that the one end face 7b' of the cage 1 'becomes the installation surface, the inner diameter portion of the cage is filled with an aluminum cage fixing jig, and a card is placed on the cage fixing jig. A ridge heater and a sheath thermocouple were inserted to adjust the temperature from 30 ° C. lower than the melting point of the fluororesin coating to 20 ° C. higher than the melting point, and the electron beam was irradiated from the electron beam irradiation window 8a ′. The irradiation atmosphere at this time is filled with nitrogen so that the inside 8b ′ of the chamber 8 ′ has an oxygen concentration of 300 ppm or less. An electron beam was irradiated from the electron beam irradiation window 8a ′. In this method, one end surface 7a ′ of the cage 1 ′ is irradiated with an electron beam, but the film on the end surface 7b ′ on the installation base 30 side is not irradiated with an electron beam. Table 3 shows the results of the same evaluation as in Example 1.

  Since the measurement of the hardness of the cage film is complicated as in Example 1, it was measured by replacing it with a flat test piece. At that time, in order to grasp the irradiation dose of the electron beam to the cage, 3 of the side 5 ′ near the irradiation window of the outer diameter surface of the cage, the middle portion 5 ″, and the side 5 ′ ″ near the installation base in advance. The same film dosimeter as in Example 1 was affixed at a total of five locations, one on each of the two end faces 7a ′ and 7b ′. Each film dosimeter on the outer diameter surface of the cage was affixed for half a circle. When a film dosimeter is attached, the cage is not heated. Using the film dosimeter after electron beam irradiation, the irradiation dose was measured in the same manner as in Example 1 using a dosimeter (FWT-92D type radiochromic film reader). The results are shown in Table 2. As a result, it was found that 40.0% of the electron beam irradiated on the outer diameter surface (5 ') on the irradiation window side was irradiated on the outer diameter surface on the side close to the installation base (5' ''). Therefore, when the outer diameter surface on the irradiation window side is irradiated with 2360 kGy, the outer diameter surface closer to the installation base is irradiated with about 944 kGy. Based on this result, a surface fluororesin film was formed on a flat plate of 30 mm × 30 mm × 2 mm thickness made of SPCC under the same conditions as in Example 1, and the same conditions as in Example 1 and a dose of about 40% thereof were obtained. Electron beams were irradiated to obtain flat plate test pieces (corresponding to the outer diameter surface and the end surface).

Comparative Example 9
It is an example which has a silver plating layer on the surface of a needle bearing retainer made of chromium molybdenum steel (SCM415) φ44 mm × width 22 mm which has been carburized, quenched and tempered. Table 3 shows the results of the same evaluation as in Example 1.

  When a PTFE film crosslinked by electron beam irradiation is applied to the cage surface, the sliding characteristics of the cage outer diameter surface are improved as shown in Examples 1 to 5. On the other hand, the unirradiated PTFE coating of Comparative Example 1 and the crosslinked PTFE coatings of Comparative Examples 2 to 5 were subjected to wear and peeling, and the base material was exposed. Since the PTFE coating on one end face of Comparative Example 8 is not irradiated, it can be easily estimated that the wear proceeds when sliding with a balance weight or a side washer. In the silver plating of Comparative Example 9, silver was eluted in the lubricating oil, and the coating was deteriorated.

  The rolling bearing retainer of the present invention and the rolling bearing having the retainer can suppress wear even under conditions of lubricating oil, high slip speed, and high surface pressure. Can be used in the field of bearings.

DESCRIPTION OF SYMBOLS 1 Needle bearing cage 2 Pocket part 3 Column part 4 Cylindrical part 5 Outer diameter surface 6 Inner diameter surface 7 End surface 8 Electron beam irradiation chamber 9 Cage fixing jig 10 Rotating shaft 11 Motor 12 Heating source 13 Control device 14 Rotary connector 15 Needle roller bearing 16 Needle roller 17 Intake pipe 18 Exhaust pipe 19 Combustion chamber 20 Piston 21 Crank shaft 22 Connecting rod 23 Rotation center shaft 24 Balance weight 25 Large end portion 26 Small end portion 27 Piston pin 28 Concave mating material 29 Load 30 Installation Stand

Claims (7)

A rolling bearing retainer comprising a cylindrical body having an outer diameter surface and an end surface adjacent to the outer diameter surface in order to hold a rolling element of a rolling bearing used in an oil lubrication environment,
The cylindrical body is composed of a base material and a sliding layer formed on the surface of the base material, and the sliding layer is a fluororesin film having at least a surface crosslinked, and is measured by the ISO14577 method. A cage for a rolling bearing, wherein the indentation hardness of the sliding layer on the outer diameter surface of the body is larger than the indentation hardness of the sliding layer on the end surface of the cylindrical body.   The rolling hardness according to claim 1, wherein the indentation hardness of the sliding layer on the outer diameter surface of the cylindrical body is 58 to 140 MPa, and the indentation hardness of the sliding layer on the end surface of the cylindrical body is 55 to 109 MPa. Bearing cage.   The rolling bearing retainer according to claim 1 or 2, wherein the indentation hardness of the sliding layer at the end face measured by the ISO14577 method is substantially the same at the left and right end faces.   The sliding layer includes a base layer containing a heat-resistant resin and a first fluororesin formed on the surface of the base material, and a second fluororesin layer formed on the base layer surface. The rolling bearing retainer according to any one of claims 1 to 3, wherein at least surfaces of the two fluororesin layers are cross-linked.   The rolling bearing cage according to any one of claims 1 to 4, wherein the sliding layer has a thickness of 10 µm or more and less than 40 µm.   The rolling bearing retainer according to any one of claims 1 to 5, wherein the base material is an iron-based metal material. In an engagement hole provided at an end of a connecting rod that supports a crankshaft that outputs rotational motion and converts linear reciprocating motion into rotational motion, or a rolling bearing attached to the crankshaft,
The rolling bearing according to any one of claims 1 to 6, wherein the cage that holds the rolling elements of the rolling bearing is the rolling bearing cage according to any one of claims 1 to 6.

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