WO2016104471A1 - Procédé de production d'élément en résine - Google Patents

Procédé de production d'élément en résine Download PDF

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Publication number
WO2016104471A1
WO2016104471A1 PCT/JP2015/085767 JP2015085767W WO2016104471A1 WO 2016104471 A1 WO2016104471 A1 WO 2016104471A1 JP 2015085767 W JP2015085767 W JP 2015085767W WO 2016104471 A1 WO2016104471 A1 WO 2016104471A1
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WO
WIPO (PCT)
Prior art keywords
molded product
resin
resin molded
plasma
resin member
Prior art date
Application number
PCT/JP2015/085767
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English (en)
Japanese (ja)
Inventor
徹 神谷
Original Assignee
株式会社ジェイテクト
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015204837A external-priority patent/JP6593635B2/ja
Application filed by 株式会社ジェイテクト filed Critical 株式会社ジェイテクト
Priority to US15/538,603 priority Critical patent/US20170348898A1/en
Priority to CN201580070911.4A priority patent/CN107108932A/zh
Priority to DE112015005774.9T priority patent/DE112015005774T5/de
Publication of WO2016104471A1 publication Critical patent/WO2016104471A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C19/00—Bearings with rolling contact, for exclusively rotary movement
    • F16C19/02—Bearings with rolling contact, for exclusively rotary movement with bearing balls essentially of the same size in one or more circular rows
    • F16C19/04—Bearings with rolling contact, for exclusively rotary movement with bearing balls essentially of the same size in one or more circular rows for radial load mainly
    • F16C19/06—Bearings with rolling contact, for exclusively rotary movement with bearing balls essentially of the same size in one or more circular rows for radial load mainly with a single row or balls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30—Parts of ball or roller bearings
    • F16C33/38—Ball cages
    • F16C33/44—Selection of substances

Definitions

  • One aspect of the present invention relates to a method for manufacturing a resin member.
  • Patent Document 1 a metal cored bar, a resin part having gear teeth formed integrally on the outer peripheral surface of the cored bar, and formed on the surface of the gear teeth by a plasma CVD method, a plasma ion implantation method, or the like.
  • a worm wheel comprising a hard carbon coating formed thereon.
  • Patent Document 2 includes a stationary ring and a rotating ring having sliding surfaces facing each other, and a mechanical surface in a water pump in which a hydrophilic surface portion is formed on each sliding surface via plasma irradiation, laser light, ultraviolet light, or the like. A seal is disclosed.
  • the surface treatment method for resin members is mainly classified into physical treatment and chemical treatment, and the treatment methods disclosed in Patent Documents 1 and 2 are included in the former physical treatment.
  • the physical treatment changes the physical properties of the surface by processing the surface of the member or forming a film.
  • the environmental load is small because the treatment has excellent sustainability (durability) and can be treated by a dry process.
  • physical processing for complicated shapes other than planar shapes has not been sufficiently established.
  • chemical treatment is a method of adding functional groups (—OH groups, —CH groups, etc.) to the surface of a resin member (polymer surface) with a solvent or gas, so it is sufficient even for complex shapes. It is valid.
  • the adsorptive power of the functional group to the polymer surface is weak, it is easily affected by external force and atmosphere, and is often inferior in durability compared to physical treatment.
  • the environmental burden is large if the solvent is not handled properly.
  • an object of one aspect of the present invention is to provide liquid resin wettability that lasts for a long period of time regardless of the shape of the resin molded product, and has a low environmental impact. It is providing the manufacturing method of a resin-made member.
  • a first step of molding a resin molded product (2) having a predetermined shape and the surface (3,4, 5, 6) of the resin molded product are treated with plasma in a vacuum.
  • a second step of roughening the surface of the resin molded product is maintained.
  • the surface of the resin molded product is brought into a high energy state by charged particles ionized by plasma excitation in vacuum.
  • the surface crystallinity can be improved and the surface density can be increased.
  • the surface roughness of the resin molded product can be increased by weak ion sputtering energy, the surface area of contact with the liquid or droplet can be increased.
  • the plasma treatment is performed in a vacuum, the charged resin particles can be spread throughout the resin molded product without escaping.
  • each surface of the member can be processed uniformly. Furthermore, since it is a dry process using plasma (physical treatment), the burden on the environment can be reduced.
  • FIG. 1 is a flowchart of a resin member manufacturing process according to an embodiment of the present invention.
  • FIG. 2 is a schematic perspective view of a resin molded product for the resin member.
  • FIG. 3 is a schematic view of an apparatus used for plasma treatment of the resin molded product.
  • FIG. 4 is a graph showing the relationship between the degree of vacuum and the discharge start voltage for each raw material gas.
  • FIG. 5 is a diagram showing a timing chart of the pulse voltage.
  • FIG. 6 is a cross-sectional view showing a rolling bearing according to an embodiment of the present invention.
  • FIG. 7 is a flowchart (modification) of the manufacturing process of the resin member according to the embodiment of the present invention.
  • FIG. 8 is a diagram for explaining a method of measuring the hardness of the soft layer.
  • FIG. 9 is a diagram showing a state of solid contact when a soft layer is formed.
  • FIG. 10 is a graph for explaining the effect of reducing the friction coefficient according to the embodiment of the present invention.
  • FIG. 11 is a diagram for explaining the effect of improving the wettability according to the embodiment of the present invention.
  • FIG. 12 is a diagram showing the hardness distribution and the amount of change at each depth from the surface of the resin member.
  • FIG. 13 is a diagram for explaining a friction test method.
  • FIG. 14 is a diagram for explaining the persistence of the friction coefficient.
  • FIG. 15 is a diagram for explaining the effect of reducing the friction coefficient.
  • FIG. 1 is a flowchart of a manufacturing process of a resin member 1 according to an embodiment of the present invention.
  • a resin molded product that becomes a main body of the resin member 1 by forming a resin material into a predetermined shape by a known molding method such as injection molding, extrusion molding, compression molding, or the like. 2 is formed (step S1).
  • thermoplastic resins examples include crystalline thermoplastic resins and thermosetting resins.
  • the crystalline thermoplastic resin examples include polyamide (PA), polyacetal (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), and liquid crystal polymer. (LCP), polytetrafluoroethylene (PTFE) and the like.
  • thermosetting resin examples include epoxy resin, phenol resin, unsaturated polyester resin, urea resin, melamine resin, diallyl phthalate resin, silicon resin, vinyl ester resin, polyimide resin, polyurethane resin, and the like.
  • the crystalline thermoplastic resin and the thermosetting resin are not limited to those exemplified, and various types can be used so as to conform to the specifications of the resin member 1.
  • FIG. 2 is a schematic perspective view of a resin molded product 2 used for the resin member 1.
  • the resin molded product 2 forms the main body of the resin member 1 used for various applications, and is molded into a shape according to the specifications of the resin member 1. That is, the shape of the resin molded product 2 shown in FIG. 2 is only an example for explaining the embodiment of the present invention.
  • Applications of the resin member 1 include, for example, vehicle sliding members such as rolling bearings and slide bearings, resin gears, various objects to be coated with water-based paints and oil-based paints, and various coating agents ( Examples include, but are not limited to, substrates that are coated with a moisture-proof coating, an antifouling coating, a water-repellent coating, and the like.
  • the resin molded product 2 includes a cylindrical member (cylindrical member in this embodiment) having a predetermined thickness, and has, for example, an outer peripheral surface 3, an inner peripheral surface 4, and end surfaces 5 and 5 at both axial ends. . At one end in the axial direction, a notch 6 is formed by selectively removing a part of the thick portion of the resin molded product 2 from the end surface 5.
  • the length L of the resin molded product 2 may be, for example, 10 mm to 30 mm.
  • the inner diameter D of the resin molded product 2 may be, for example, 5 mm ( ⁇ 5) to 20 mm ( ⁇ 20).
  • the heat resistant temperature of the resin molded product 2 may be, for example, 80 ° C. to 150 ° C.
  • FIG. 3 is a schematic diagram of the vacuum chamber device 7 used for the plasma treatment of the resin molded product 2.
  • a susceptor 9 is disposed below the chamber 8 of the vacuum chamber device 7.
  • the susceptor 9 incorporates a heater 10.
  • an exhaust line 12 provided with a vacuum pump 11 in the middle is connected to the lower portion of the chamber 8.
  • the vacuum pressure region used in this embodiment is, for example, 1 ⁇ 10 ⁇ 1 Pa to 1 ⁇ 10 ⁇ 2 Pa.
  • a source gas supply line 13 for supplying source gas into the chamber 8 is connected to the top of the chamber 8.
  • a plurality of source gas supply lines 13 may be provided when a plurality of source gas is supplied.
  • wiring is connected to the top 14 of the chamber 8, and the top 14 facing the susceptor 9 also serves as an electrode.
  • a DC bias is applied between the top 14 and the susceptor 9.
  • the distance (distance between electrodes) between the top portion 14 and the susceptor 9 is, for example, 80 mm to 400 mm.
  • the source gas is supplied from the source gas supply line 13 while exhausting the gas in the chamber 8 from the exhaust line 12 by driving the vacuum pump 11.
  • the pressure in the chamber 8 is maintained at a medium vacuum of 40 Pa to 90 Pa, and an inert gas is supplied as a source gas.
  • discharge ignition plasma excitation
  • the inert gas is turned into plasma.
  • the applied voltage at the time of discharge ignition is, for example, 300 V to 600 V, and preferably 400 V to 500 V.
  • the temperature of the heater 10 is, for example, 30 ° C. to 150 ° C.
  • the inert gas is supplied as the source gas in the initial stage of plasma treatment (during discharge ignition)
  • the discharge start voltage of air is 500 V to 600 V
  • the discharge start voltage of the inert gas (He, Ar) is 400 V. It is about 450V.
  • the pressure in the chamber 8 becomes about several Pa. Under such a low vacuum, gas may be released from the resin molded product 2 at the time of discharge ignition, and the resin molded product 2 may be deteriorated.
  • an inert gas as a raw material gas for discharge ignition, discharge ignition can be favorably performed under a medium vacuum.
  • the inert gas N 2 (nitrogen) can be used in addition to a rare gas such as He or Ar.
  • the discharge ignition is completed, it is a transition from the initial stage to the steady stage.
  • the plasma excitation state is maintained while the vacuum degree of the chamber 8 is maintained at medium vacuum, and the source gas is replaced with air from the inert gas (step S4).
  • a pulse voltage is applied between the top 14 of the chamber 8 and the susceptor 9 by ON / OFF control of a voltage lower than the discharge start voltage.
  • air is turned into plasma (non-equilibrium plasma), and the resin molded product 2 is subjected to plasma treatment with the charged particles ionized at that time (step S5).
  • the plasma is continuously generated in the chamber 8 due to the transition from the initial stage, so that air can be turned into plasma at a relatively low voltage even under a medium vacuum. .
  • the duration of the steady stage is, for example, 10 minutes to 15 minutes. If the plasma treatment time is less than 10 minutes, it is difficult to obtain a sufficient treatment effect. On the other hand, when the plasma treatment time exceeds 15 minutes, the temperature and surface roughness of the resin molded product 2 may be excessively increased.
  • the pulse width of the pulse voltage is, for example, 0.2 ms to 1 ms, and preferably 0.2 ms to 0.25 ms.
  • the pulse frequency is, for example, 0.1 kHz to 0.5 kHz, preferably 0.4 kHz to 0.5 kHz. If the pulse frequency is less than 0.1 kHz, it is difficult to obtain a sufficient processing effect. On the other hand, when the pulse frequency exceeds 0.5 kHz, the temperature of the resin molded product 2 may be excessively increased. Further, the temperature of the heater 10 in the steady stage is, for example, 60 ° C. to 120 ° C.
  • the resin member 1 is obtained by removing the resin molded product 2 from the chamber 8.
  • the surface (the outer peripheral surface 3, the inner peripheral surface 4, the end surface 5 and the notch portion 6) of the resin molded product 2 is obtained by charged particles ionized from O 2 , CO 2 , H 2 O and the like constituting the air. ) Is in a high energy state. Thereby, the crystallinity of the surface of the resin molded product 2 can be improved and the surface density can be increased.
  • the surface roughness of the resin molded product 2 can be increased by weak ion sputtering energy, the surface area of contact with the liquid or droplet can be increased.
  • the contact angle of the surface of the resin molded product 2 with respect to the liquid can be made less than 70% compared to before the plasma treatment.
  • the plasma treatment is performed in a vacuum, the charged resin particles can be spread over the entire resin molded product 2 without escaping. For this reason, it is possible to uniformly treat even a hollow portion such as the inner peripheral surface 4 or the cutout portion 6 of the resin molded product 2. Furthermore, since it is a dry process using plasma (physical treatment), the burden on the environment can be reduced.
  • the resin molded product 2 made of a polymer material mainly composed of C (carbon atoms), H (hydrogen atoms), and O (oxygen atoms) is air (including O 2 , CO 2 , and H 2 O). It is processed with plasma using. Therefore, a lipophilic (—CH group) or hydrophilic (—OH group) functional group can be imparted to the surface of the resin molded product 2 during the plasma treatment.
  • FIG. 6 is a cross-sectional view showing a rolling bearing 21 according to an embodiment of the present invention.
  • the rolling bearing 21 includes a pair of race members, an inner ring 23 and an outer ring 24, which define an annular region 22 between them, and a plurality of rolling elements that are disposed in the region 22 and roll relative to the inner ring 23 and the outer ring 24.
  • a cage 26 that holds each ball 25, grease G filled in the region 22, and a pair of annular seal members 27 that are fixed to the outer ring 24 and are in sliding contact with the inner ring 23. , 28.
  • Each of the sealing members 27 and 28 includes annular core bars 29 and 29 and annular rubber bodies 30 and 30 baked on the core bars 29 and 29.
  • Each of the seal members 27 and 28 is fitted and fixed to groove portions 31 and 31 formed on both end surfaces of the outer ring 24 at the outer peripheral portion, and groove portions 32 and 32 formed on both end surfaces of the inner ring 23 at the inner peripheral portion. It is fitted and fixed.
  • the grease G is sealed so as to be substantially full in the region 22 defined by the pair of seal members 27 and 28 between the two wheels 23 and 24.
  • the grease G can be spread over the sliding surface of the cage 26. Thereby, since the quantity of grease G can be reduced and the stirring resistance of grease G can be reduced, the bearing torque of the rolling bearing 21 can be reduced.
  • the present invention is not limited to the above-described embodiment, and can be implemented in other embodiments.
  • the source gas used in the initial stage and the steady stage is not limited to the inert gas and air described above, and other gases may be used as long as the effects of the present invention can be exhibited.
  • thermal plasma can be used instead of non-equilibrium plasma, and it is not necessary to generate plasma by pulse discharge.
  • plasma may be generated by RF (Radio Frequency) discharge.
  • step S3 after performing discharge ignition with an inert gas (step S3), the raw material gas was immediately replaced with air from the inert gas (step S4).
  • step S3 ′ of FIG. 7 the soft layer 15 is formed on the surface of the resin molded product 2 by pre-processing the resin molded product 2 with plasma of an inert gas prior to the replacement with the source gas. You may form (refer FIG. 8). More specifically, after performing discharge ignition with an inert gas, the plasma state of the inert gas is continued for a predetermined time.
  • the ionized inert gas accelerates and collides with the target (not shown), and the substance is sputtered from the target and collides with the resin molded product 2.
  • sputtering with an inert gas is performed, the polymer chain on the surface of the resin molded product 2 is broken (weak deterioration), and the soft layer 15 is formed at the broken portion.
  • the inert gas used for discharge ignition may be used as it is, or the inert gas used for discharge ignition may be switched to another inert gas.
  • the preprocessing time may be, for example, 300 seconds to 600 seconds. If it is less than 300 seconds, the polymer chain on the surface of the resin molded product 2 may not be sufficiently broken. On the other hand, in the long-time treatment exceeding 600 seconds, there is a possibility that excessive deterioration occurs on the surface of the resin molded product 2.
  • the soft layer 15 thus formed is formed, for example, in a range of less than 50 ⁇ m (preferably 0 ⁇ m to 20 ⁇ m) from the surface (treated surface) of the resin molded product 2.
  • the hardness of the soft layer 15 is reduced by, for example, 40% or more compared to the untreated portion (hard layer not subjected to the sputtering treatment) of the resin molded product 2.
  • the hardness at the time of 400 nm to 600 nm indentation measured using a thin film hardness meter (indentation load: 1000 ⁇ N) may be 0.05 GPa to 0.13 GPa.
  • the thin-film hardness meter is measured by cutting the processed resin molded product 2 and sequentially pushing the indenter of the thin-film hardness meter into the cross section in the depth direction from the processing surface. Just do it.
  • the amount of lubricating oil between the resin member 1 (resin molded product 2) and the mating member 17 is temporarily reduced as shown in FIG. Even if solid contact occurs between the manufactured member 1 and the mating member 17, the impact caused by the contact of the mating member 17 can be mitigated by receiving the mating member 17 while sliding it with the soft layer 15. As a result, since the coefficient of friction between the resin member 1 and the mating member 17 can be kept low for a long period of time, the seizure resistance of the resin member 1 can be improved. That is, according to this modified example, as shown in FIG.
  • the hardness of the surface layer of the resin member 1 is controlled. By doing so, the effect of reducing the friction coefficient ⁇ in the boundary lubrication region A can be enjoyed (two-dot chain line). Since the temperature reduction of the sliding portion of the resin member 1 can be suppressed by this low friction, an inexpensive material having a relatively low heat-resistant temperature can be applied as the material of the resin member 1.
  • Example 1 a sample to be processed (molded product) was produced based on FIG. Sample preparation conditions are as follows.
  • Resin material PA (polyamide) 66 Length L: 25mm Inner diameter D: ⁇ 15
  • plasma processing was performed on the obtained sample to be processed following the above method.
  • Ar was used in the initial stage and air was used in the steady stage.
  • a network structure with an interval of 50 ⁇ m to 200 ⁇ m is given to the surface of the sample to be processed, and the network structure is constituted by a convex shape having a height of 0.1 ⁇ m to 3.0 ⁇ m from the surface.
  • the interval between the mesh structures and the height of the protrusions were confirmed by photographing the surface of the sample after the plasma treatment with a scanning electron microscope (SEM) and based on the scale of the obtained image. Since the surface area of the sample is increased by the network structure, it has been found that the contact angle of the liquid can be reduced by the following equation (1) known as the Wenzel equation.
  • Example 2 A resin plate made of PA (polyamide) 66 was prepared, and plasma treatment was performed in accordance with the above method.
  • Ar was used in the initial stage and air was used in the steady stage.
  • the surface of the resin plate was subjected to sputtering treatment (pretreatment) by continuing the Ar gas plasma state for 300 seconds.
  • the hardness at each depth position of 0.3 ⁇ m, 1 ⁇ m, 50 ⁇ m, 200 ⁇ m, 1200 ⁇ m, 1500 ⁇ m and 2000 ⁇ m from the treated surface of the resin plate is measured with a thin film hardness meter (indentation load: 1000 ⁇ N).
  • the results are shown in FIG. From FIG. 12, it was found that a soft layer having a reduced hardness was formed at depths of at least 0.3 ⁇ m and 1 ⁇ m compared to before the plasma treatment.
  • the hardness was higher than before the plasma treatment. It is considered that this is because some energy (microvibration, thermal energy, etc.) is applied to the resin plate by sputtering or the like, and as a result, the resin is recrystallized (recondensed) immediately below the soft layer.
  • FIG. 14 is a diagram for explaining the persistence of the friction coefficient.
  • FIG. 15 is a diagram for explaining the effect of reducing the friction coefficient.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un procédé comprenant, dans une première étape, la formation d'un produit moulé en résine ayant une forme prédéterminée, suivie, dans une seconde étape, du traitement au plasma de la surface du produit moulé en résine sous vide pour fournir des protubérances et des renfoncements sur la surface du produit moulé en résine. Dans la seconde étape, l'allumage par décharge est exécuté dans un gaz inerte pour générer le plasma, et ensuite, tout en maintenant le degré de vide à ce stade, un gaz matière première est substitué à l'air.
PCT/JP2015/085767 2014-12-24 2015-12-22 Procédé de production d'élément en résine WO2016104471A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/538,603 US20170348898A1 (en) 2014-12-24 2015-12-22 Resin member production method
CN201580070911.4A CN107108932A (zh) 2014-12-24 2015-12-22 树脂部件生产方法
DE112015005774.9T DE112015005774T5 (de) 2014-12-24 2015-12-22 Harzbauteilproduktionsverfahren

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014-260519 2014-12-24
JP2014260519 2014-12-24
JP2015-204837 2015-10-16
JP2015204837A JP6593635B2 (ja) 2014-12-24 2015-10-16 樹脂製部材の製造方法

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WO2016104471A1 true WO2016104471A1 (fr) 2016-06-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018097146A1 (fr) * 2016-11-24 2018-05-31 日本ゼオン株式会社 Feuille d'adhésif, et verre feuilleté

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5614534A (en) * 1979-07-16 1981-02-12 Shin Etsu Chem Co Ltd Surface treatment of plastic molded product
JPS5778426A (en) * 1980-10-31 1982-05-17 Shin Etsu Chem Co Ltd Treatment of vinyl chloride resin molding
JPS5884827A (ja) * 1981-11-16 1983-05-21 Agency Of Ind Science & Technol 改質された塩化ビニル系樹脂成形品
JPS62132940A (ja) * 1985-12-04 1987-06-16 Sumitomo Electric Ind Ltd 高分子基材へのプラズマ重合薄膜形成方法
JPS63215737A (ja) * 1987-03-04 1988-09-08 Asahi Chem Ind Co Ltd 表面を改質した成形体の製造法
JPH08118546A (ja) * 1994-10-27 1996-05-14 Tokai Rubber Ind Ltd 積層体およびその製法
JP2012077253A (ja) * 2010-10-05 2012-04-19 Nsk Ltd 表面改質方法、樹脂製部材、シール装置及び車輪支持用転がり軸受装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5614534A (en) * 1979-07-16 1981-02-12 Shin Etsu Chem Co Ltd Surface treatment of plastic molded product
JPS5778426A (en) * 1980-10-31 1982-05-17 Shin Etsu Chem Co Ltd Treatment of vinyl chloride resin molding
JPS5884827A (ja) * 1981-11-16 1983-05-21 Agency Of Ind Science & Technol 改質された塩化ビニル系樹脂成形品
JPS62132940A (ja) * 1985-12-04 1987-06-16 Sumitomo Electric Ind Ltd 高分子基材へのプラズマ重合薄膜形成方法
JPS63215737A (ja) * 1987-03-04 1988-09-08 Asahi Chem Ind Co Ltd 表面を改質した成形体の製造法
JPH08118546A (ja) * 1994-10-27 1996-05-14 Tokai Rubber Ind Ltd 積層体およびその製法
JP2012077253A (ja) * 2010-10-05 2012-04-19 Nsk Ltd 表面改質方法、樹脂製部材、シール装置及び車輪支持用転がり軸受装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018097146A1 (fr) * 2016-11-24 2018-05-31 日本ゼオン株式会社 Feuille d'adhésif, et verre feuilleté

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