Resin composition and sliding member

Information

  • Patent Grant
  • 11352581
  • Patent Number
    11,352,581
  • Date Filed
    Thursday, November 16, 2017
    6 years ago
  • Date Issued
    Tuesday, June 7, 2022
    2 years ago
Abstract
A resin composition includes: a binder resin made of a thermosetting resin; an additive dispersed in the binder resin, wherein the additive includes PTFE (polytetrafluoroethylene), and at least one of graphite and MoS2, an average particle size of each of the additive is less than 10 μm, and an average particle size of the PTFE is larger than the average particle size of graphite and MoS2.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Stage Application of International Application No. PCT/JP2017/041336, filed on Nov. 16, 2017, which claims priority to Japanese Application No. 2016-224316, filed on Nov. 17, 2016. The entire disclosures of the above applications are incorporated herein by reference.


TECHNICAL FIELD

The present invention relates to a sliding member.


RELATED ART

To improve characteristics of a sliding surface, a sliding material with a resin coating layer is known, in which PTFE, graphite, and MoS2 are used as additives in a binder resin (refer to JP 2002-310345 and JP 2008-56750).


In the technology disclosed in JP 2002-310345 and JP 2008-56750, a problem exists in that a solid lubricant is liable to fall off or cleave under a high-load state, as a result of which the sliding surface becomes rougher. When the sliding surface becomes rough, formation of an oil film is impeded, particularly where an amount of oil present is low, or in a dry environment where a supply of lubricating oil is insufficient. Under such circumstances, abrasion and seizure resistance decreases.


The present invention provides a technique for improving wear and seizure resistance under a high load state in an environment where a supply of lubricating oil supply is insufficient.


SUMMARY

The present invention provides a resin composition including: a binder resin made of a thermosetting resin; an additive dispersed in the binder resin, wherein the additive includes PTFE (polytetrafluoroethylene), and at least one of graphite and MoS2, where an average particle size of each of the additive is less than 10 μm, and an average particle size of the PTFE is larger than the average particle size of graphite and MoS2.


The binder resin may include at least one of Polyamide-imide and Polyimide.


The binder resin may be Polyamide-imide.


A content of the binder resin may be 50 to 80 vol %.


A content of the PTFE is higher than a content of the MoS2.


The content of the MoS2 is 0 to 10 vol %.


The additive may include a hard particle.


The present invention further provides a sliding member including: a basic material; and a coating layer made of the resin composition.


Advantageous Effect

According to the present invention, wear and seizure resistance can be improved under a high load state in an environment where a supply of lubricating oil is insufficient.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a schematic cross-sectional view showing the structure of compressor 1 according to one embodiment.



FIG. 2 illustrates an example of the positional relationship between swash plate 3 and shoes 5.



FIG. 3 illustrates an exemplary cross-sectional structure of swash plate 3.



FIG. 4 shows a surface pressure measured in a contact resistance test.



FIGS. 5A-5C show states of sliding surfaces before and after sliding tests.





DETAILED DESCRIPTION
1. Configuration


FIG. 1 is a schematic cross-sectional view showing the structure of compressor 1 according to one embodiment of the present invention. Compressor 1 is a swash plate type compressor. Compressor 1 includes shaft 2, swash plate 3, piston 4 and shoe 5. Shaft 2 is rotatably supported relative to a housing (not shown in the figures). Swash plate 3 is fixed at an oblique angle relative to the axis of rotation of shaft 2. Swash plate 3 is an example of the sliding member according to the present invention. Piston 4 reciprocates in a cylinder bore (not shown in the figures) provided in the housing. Shoe 5 is provided between swash plate 3 and piston 4 and slides with each of swash plate 3 and piston 4, respectively. In shoe 5, the surface that slides with swash plate 3 is substantially flat, and the surface sliding with piston 4 has a dome-like (hemispherical) shape. Shoe 5 is an example of a mating member that slides on the sliding member according to the present invention. The rotation of shaft 2 is converted to the reciprocating motion of piston 4 by swash plate 3.



FIG. 2 illustrates an example of the positional relationship between swash plate 3 and shoes 5. FIG. 2 is a view from a direction perpendicular to the sliding surface. Swash plate 3 is disk-shaped overall, and has a hole at its center. Viewed from swash plate 3, shoe 5 performs rotational movement on the sliding surface. Here, “rotational movement” refers to a movement by which shoe 5 defines a circular trajectory relative to swash plate 3.



FIG. 3 illustrates an exemplary cross-sectional structure of swash plate 3. FIG. 3 is a schematic view showing a structure in cross section perpendicular to the surface that slides with shoe 5. Swash plate 3 has a substrate 31, coating layer 32, and coating layer 33. Coating layer 32 and coating layer 33 both slide on shoe 5. Each of coating layer 32 and coating layer 33 are examples of the coating layer according to the present invention. The base material 31 is formed to be disk-shaped with a hole at its center. The base material is made of an alloy satisfying the required characteristics, for example, the material is an iron-based, copper-based, or aluminum-based alloy. From the viewpoint of preventing adhesion with shoe 5, swash plate 3 is preferably made of a material different from that of shoe 5.


Coating layer 32 is formed to improve the characteristics of the sliding surface of swash plate 3. Coating layer 32 is made of a resin composition. The resin composition includes a binder resin and an additive dispersed in the binder resin. The binder resin is made of, for example, a thermosetting resin. At least one of polyamideimide (PAI), polyamide (PA), and polyimide (PI), epoxy, and phenol is used as the thermosetting resin, for example. Among these, the binder resin preferably includes at least one of PAI and PI. For example, the content of the binder resin in the resin composition is preferably 50 to 80 vol %. More preferably, the content of the binder resin is more than 60 vol %. More preferably, the upper limit of the content of the binder resin is 75 vol %.


A solid lubricant is used as the additive. The solid lubricant is added to improve lubricating properties, in other words, to reduce a coefficient of friction. For example, the resin composition includes 20 to 50 vol % of solid lubricant in total. PTFE (polytetrafluoroethylene) is used as the solid lubricant. Furthermore, this resin composition includes, in addition to PTFE, at least one of graphite (Gr) and MoS2. The content of MoS2 is preferably less than the content of PTFE. For example, the content of PTFE 10 to 30 vol %, and more preferably 15 to 25 vol %. The content of MoS2 is 0 to 10 vol %, preferably 0 to 4 vol % (that is, MoS2 may not be included). The content of graphite is preferably 0 to 20 vol %, more preferably 10 to 20 vol %. Moreover, it is preferable that the content of MoS2 is less than the content of graphite.


The average particle diameter of the additive added to the binder resin is preferably less than 10 μm, and more preferably, equal to or less than 5 μm, in order to enhance the smoothness of the sliding surface and to assist the formation of an oil film. Here, the average particle diameter means the 50% diameter (median diameter) in the distribution of the sphere equivalent diameter obtained by the laser diffraction method in the state of the raw material before mixing with the binder resin. When the average particle diameter of the additive is less than 10 μm, the sliding surface is maintained smooth, in contrast to where the average particle diameter of the additive is equal to or less than 10 μm, and as a result formation of an oil film is enhanced. Therefore, transition from boundary lubrication to mixed lubrication or fluid lubrication is facilitated, and enhanced lubrication is easily obtained even under severe conditions such as low oil content and high load.


The average particle size of PTFE is preferably larger than either the average particle size of graphite or the average particle size of MoS2. The inventors of the present invention hypothesize that by using PTFE having an average particle diameter larger than that of graphite and MoS2, the PTFE is stretched on the sliding surface to cover the graphite or MoS2, whereby smoothness of the sliding surface is easily maintained.


The resin composition may further include hard particles as the additive. As the hard particle, at least one of an oxide, a nitride, a carbide, and a sulfide is used, for example. The average particle size of the hard particles is preferably less than 10 μm, and more preferably smaller than the average particle size of PTFE.


Coating layer 33 is also formed using the same resin composition as coating layer 32. In the substrate 31, the surface that acts as the sliding surface, that is, the surface on which coating layer 32 is formed and the surface on which coating layer 33 is formed are substantially flat. The surface of the substrate 31 may be roughened to enhance the adhesion to coating layer 32. In addition, an intermediate layer may be formed between the substrate 31 and coating layer 32.


The present invention is not limited to the above embodiment and various modifications can be applied to the embodiment. For example, the sliding member having a coating layer formed using the resin composition according to the present embodiment is not limited to a swash plate for a compressor. The sliding member may be a shoe for a compressor, or a half bearing, a bush, or a thrust washer used in an engine.


2. Experiment Examples

The present inventors manufactured test pieces of the sliding member under various conditions. The present inventors evaluated their characteristics. Cast iron was used as the base material of the sliding member. The base material was processed to have the shape of the swash plate shown in FIG. 1. The coating layer was formed on this base material, and was made of the resin composition described in Table 1. PAI was used as the binder resin. Experiment Example 3 is an example where the average particle size of MoS2 is larger than the average particle size of PTFE.













TABLE 1









PTFE
Gr.
MoS2















binder

average

average

average



resin

particle

particle

particle



vol
vol
size
vol
size
vol
size



%
%
(μm)
%
(μm)
%
(μm)


















Experiment
Val.
16
5
18
2
2
2


Example 1


Experiment
Val.
20
5
18
2
not



Example 2





included


Experiment
Val.
11
5
16
2
19 
20 


Example 3









First, the abrasion resistance test was performed on the test pieces of the above three experiment examples. The test conditions of the abrasion resistance test were as follows.

    • Test equipment: High pressure atmosphere friction and wear tester
    • Speed: 40 m/sec
    • Surface pressure: 4 to 12 MPa (increased incrementally by 2 MPa/3 min)
    • Time: Hold for 1 hour at maximum surface pressure
    • Atmosphere: refrigerant and poor lubrication
    • Counterpart material: Bearing steel


The present inventor observed the sliding surface of the test pieces after the test, and confirmed whether the coating layer was worn or not. Although abrasion occurred in Experiment Example 3, no abrasion was found in Experiment Examples 1 and 2. Thus, compared with Experiment Example 3, Experiment Examples 1 and 2 showed improved wear resistance.


Furthermore, the present inventors performed a seizure resistance test on the test pieces of Experiment Examples 1 and 2. The test conditions of the seizure resistance test were as follows.

    • Testing device: Oil spray type poor lubrication tester
    • Speed: 6.3 m/sec
    • Surface pressure: 2 to 20 MPa (incremental increase: 2 MPa/min.)
    • Time: up to 10 min.
    • Lubrication method: Spray
    • Lubricating oil: refrigeration oil
    • Counterpart material: Bearing steel



FIG. 4 shows the surface pressure measured in the contact resistance test. While seizure occurred in the test piece of Experiment Example 3 at a surface pressure of 10 MPa, no seizure occurred in the test pieces of Experiment Examples 1 and 2 even at a maximum surface pressure of 20 MPa of the test apparatus. Thus, compared with Experiment Example 3, Experiment Examples 1 and 2 showed improved seizure resistance.


Furthermore, the present inventors performed a sliding test on the test pieces of Experiment Examples 1 and 2, and measured the surface roughness of the sliding surface before and after the test using a surface roughness meter (SP81B manufactured by Kosaka Laboratory). Further, the surface was observed with an electron microscope. The test conditions of the sliding test were the same as those of the seizure resistance test described above.



FIGS. 5A-5C show states of the sliding surfaces before and after sliding tests. FIG. 5A shows Experiment Example 1, FIG. 5B shows Experiment Example 2, and FIG. 5C shows Experiment Example 3. It is of note that the surface roughness is measured according to the ten-point average roughness RzJIS defined in JIS B 0601: 2001. While the surface roughness increased in Experiment Example 3 during the sliding test, the surface roughness decreased in Experiment Examples 1 and 2 during the sliding test. In other words, while the surface became rougher in Experiment Example 3 after use, the surface became smoother in Experiment Examples 1 and 2 after use.

Claims
  • 1. A resin composition comprising: a binder resin made of a thermosetting resin; andgreater than or equal to 10 vol. % to less than or equal to 30 vol. % of PTFE (polytetrafluoroethylene), the PTFE being dispersed in the binder resin, an average particle size of the PTFE being less than 10 μm.greater than 0 vol. % to less than or equal to 4 vol. % of MoS2, the MoS2 being dispersed in the binder resin, an average particle size of the MoS2 being less than 10 μm and less than the average particle size of the PTFE, andgreater than or equal to 10 vol. % to less than or equal to 20 vol. % of graphite, the graphite being dispersed in the binder resin, an average particle size of the graphite being less than 10 μm and less than the average particle size of the PTFE.
  • 2. The resin composition according to claim 1, wherein the binder resin includes at least one of polyamide-imide and polyimide.
  • 3. The resin composition according to claim 2, wherein the binder resin is polyamide-imide.
  • 4. The resin composition according to claim 1, wherein the content of the binder resin is 50 to 80 vol %.
  • 5. The resin composition according to claim 1, further comprising an additive dispersed in the binder resin, whereinthe additive includes a hard particle selected from the group consisting of: oxides, nitrides, carbides, sulfides, and combination thereof.
  • 6. A sliding member comprising: a base material; anda coating layer made of the resin composition according to claim 1.
  • 7. The sliding member of claim 6, wherein the base material is one of an iron-based, copper-based, and aluminum-based alloy.
Priority Claims (1)
Number Date Country Kind
JP2016-224316 Nov 2016 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2017/041336 11/16/2017 WO 00
Publishing Document Publishing Date Country Kind
WO2018/092856 5/24/2018 WO A
US Referenced Citations (24)
Number Name Date Kind
4898905 Kawakami Feb 1990 A
5427698 Hirokawa Jun 1995 A
5486299 Fuwa et al. Jan 1996 A
5700093 Hiramatsu et al. Dec 1997 A
6305847 Tanaka Oct 2001 B1
20030111511 Kanayama et al. Jun 2003 A1
20040259741 Sugioka Dec 2004 A1
20050139064 Hakamata Jun 2005 A1
20080283021 Maier Nov 2008 A1
20080312357 Tanaka Dec 2008 A1
20100261625 Hakamata Oct 2010 A1
20110052112 Yamane Mar 2011 A1
20110082059 Iwata Apr 2011 A1
20120101011 Makino Apr 2012 A1
20120149611 Yamaguchi et al. Jun 2012 A1
20130159764 Adar Jun 2013 A1
20130247699 Nomura et al. Sep 2013 A1
20130337271 Yoshikawa et al. Dec 2013 A1
20140301880 Horibe et al. Oct 2014 A1
20140303050 Tomikawa et al. Oct 2014 A1
20150057199 Yamasaki Feb 2015 A1
20150330376 Taniyama et al. Nov 2015 A1
20150337824 Taniyama Nov 2015 A1
20160251589 Kishi et al. Sep 2016 A1
Foreign Referenced Citations (30)
Number Date Country
103415604 Nov 2013 CN
1281881 Feb 2003 EP
1548067 Jun 2005 EP
2762552 Aug 2014 EP
H07-097517 Apr 1995 JP
H08-104803 Apr 1996 JP
H08-199116 Aug 1996 JP
H09-236125 Sep 1997 JP
H11-246823 Sep 1999 JP
2002-310345 Oct 2002 JP
2002-310345 Oct 2002 JP
2005-146366 Jun 2005 JP
2005-305395 Nov 2005 JP
2008-056750 Mar 2008 JP
2008-259965 Oct 2008 JP
2009-068390 Apr 2009 JP
2010-196813 Sep 2010 JP
2011-208612 Oct 2011 JP
2011-208613 Oct 2011 JP
2011-213761 Oct 2011 JP
2016-160293 Sep 2016 JP
02-075172 Sep 2002 WO
02075172 Sep 2002 WO
WO-2009-041653 Apr 2009 WO
2012-074107 Jun 2012 WO
2012-111774 Aug 2012 WO
2013-047800 Jan 2013 WO
2013-051340 Apr 2013 WO
WO-2014-103073 Jul 2014 WO
WO-2014103067 Jul 2014 WO
Non-Patent Literature Citations (18)
Entry
The Best Dispersibility PTFE Micropowder | PTFE Solid Powder Lubricants KT/KTL Series | Kitamura Limited (kitamuraltd.jp) available online date unknown (Year: 2021).
Untitled (quatek.com.cn) KTL KT Series List 1 Kitamura Limited polytetrafluoroethylene solid powder lubricants available online date unknown (Year: 2021).
By The Best Dispersibility PTFE Micropowder | PTFE Solid Powder Lubricants KT/KTL Series | Kitamura Limited (kitamuraltd.jp) (Year: 2005).
Effects of Solid Lubricants on PA6 Li Du Xin, Li Wen Juan, Xie Ying, Li Xiang Xiang Journal of Applied Polymer Science vol. 124 4239-4248 (2012) (Year: 2012).
Generally Molybdenum Disulfide as a Lubricant: A review of the fundamental knowledge W O Winer Dept. of Mechanical Engineering (1967) Wear, 10 (1967) 422-452 (Year: 1967).
Tribological Studies to Analyze the Effect of Solid Lubricant Particle Size on Friction and Wear Behaviour of Ti GA1 4V Alloy Rakesh Kumar Gunda, Suresh Kumar Reddy Narala Surface Coatings Technology 308 (2016) 203-212 (Year: 2016).
Japanese Office Action for Application No. 2016-224316 dated Mar. 3, 2020 with English translation (4 pages).
Japanese Office Action for Application No. 2016-224316 dated Sep. 1, 2020 with English translation (6 pages).
Extended European Search Report for Patent Application No. EP 17872673.3 dated Jun. 2, 2020 (7 pages).
Korean Office Action for corresponding Korean Application No. 10-2019-7014779 dated May 15, 2020 with English translation (12 pages).
Korean Office Action for corresponding Korean Application No. 10-2019-7014779 dated Dec. 23, 2020 with English translation (11 Pages).
Chinese Office Action for corresponding Chinese Application No. 201780069675.3 dated Dec. 28, 2020 with English translation (12 Pages).
European Office Action for corresponding European Application No. 17872673.3 dated Feb. 8, 2021 (5 Pages).
Chinese Office Action for corresponding Chinese Application No. 201780069675.3 dated Jun. 1, 2021 with English translation (10 Pages).
Office Action for Patent Application No. KR 10-2019-7014777 dated May 27, 2020 (9 pages).
Office Action for Patent Application No. JP 2016-224317 dated Jun. 2, 2020 (7 pages).
Extended European Search Report for Patent Application No. EP 17870663.6 dated Jun. 17, 2020 (7 pages).
Office Action for Patent Application No. JP 2016-224317 dated Feb. 2, 2021 (21 pages).
Related Publications (1)
Number Date Country
20190309235 A1 Oct 2019 US