JP6114180B2 - Coating composition for sliding member - Google Patents
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- JP6114180B2 JP6114180B2 JP2013271133A JP2013271133A JP6114180B2 JP 6114180 B2 JP6114180 B2 JP 6114180B2 JP 2013271133 A JP2013271133 A JP 2013271133A JP 2013271133 A JP2013271133 A JP 2013271133A JP 6114180 B2 JP6114180 B2 JP 6114180B2
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- 239000008199 coating composition Substances 0.000 title claims description 88
- 239000000843 powder Substances 0.000 claims description 48
- 229920002379 silicone rubber Polymers 0.000 claims description 48
- 239000004945 silicone rubber Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 33
- 239000000314 lubricant Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000010687 lubricating oil Substances 0.000 claims description 18
- 239000004962 Polyamide-imide Substances 0.000 claims description 17
- 229920006015 heat resistant resin Polymers 0.000 claims description 17
- 229920002312 polyamide-imide Polymers 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- -1 polysiloxane Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 42
- 239000000203 mixture Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 230000001603 reducing effect Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
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- 238000005461 lubrication Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010705 motor oil Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001060 Gray iron Inorganic materials 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000010718 automatic transmission oil Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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- Paints Or Removers (AREA)
Description
本発明は、摺動部材用被膜組成物及び該被膜組成物を摺動面に備えた摺動部材に関する。 The present invention relates to a coating composition for a sliding member and a sliding member provided with the coating composition on a sliding surface.
自動車では、エンジン、トランスミッションなど様々な機器に摺動部材が用いられており、そのような摺動部材の摺動特性を向上させるために様々な開発がされている。摺動部材の摩擦係数を低減させることは自動車の燃費の向上にも繋がるので、特に重要視されている。 In automobiles, sliding members are used in various devices such as engines and transmissions, and various developments have been made to improve the sliding characteristics of such sliding members. Reducing the coefficient of friction of the sliding member is particularly important because it leads to an improvement in the fuel consumption of the automobile.
これらの摺動部材は、潤滑油を用いた湿式条件で使用されるが、近年、エンジンの小型化・軽量化への要求が高まり、ピストン周りにおいてもピストンスカートの面積の減少や、ピストンスカート表面とシリンダボア間のクリアランスの減少を招くなど、摺動部材の潤滑状態はますます厳しいものになってきている。 These sliding members are used under wet conditions using lubricating oil, but in recent years, the demand for smaller and lighter engines has increased, and the area of the piston skirt around the piston has decreased, and the surface of the piston skirt has increased. The lubrication state of the sliding member is becoming increasingly severe, such as reducing the clearance between the cylinder bore and the cylinder bore.
摺動部材の摩擦係数を低減させるための一つの手段として、樹脂の被膜組成物がピストンスカート部などの摺動部材に適用されている。このような被膜組成物は、多くの場合、耐熱性樹脂及び添加剤を含む。添加剤としては、アルミナが耐摩耗性を向上させることや、二硫化モリブデン、グラファイトやPTFE(ポリテトラフルオロエチレン)が摩擦特性を向上させることが知られている。また、添加剤としてシリコーンゴムパウダーを用いた摺動部材用被膜組成物も知られている。 As one means for reducing the friction coefficient of the sliding member, a resin coating composition is applied to the sliding member such as a piston skirt. Such coating compositions often contain a heat resistant resin and an additive. As additives, it is known that alumina improves wear resistance, and molybdenum disulfide, graphite and PTFE (polytetrafluoroethylene) improve friction characteristics. Also known are coating compositions for sliding members using silicone rubber powder as an additive.
例えば、特許文献1には、繊維状物質、結合剤及び摩擦調整剤を含む摩擦材組成物において、結合剤として熱硬化性樹脂とゴム組成物との混合結合剤を使用し、また摩擦調整剤の一部がカシューダストと平均粒径が0.1〜50μmのシリコーンゴムパウダーとの混合物を造粒したものであり、かつカシューダスト100重量部に対してシリコーンゴムパウダーを0.05〜31重量部の割合で含有する摩擦材組成物が記載されている。
For example,
また、特許文献2には、熱可塑性樹脂中に、潤滑剤としてのシリコーンオイル及び/又はシリコーンポリマー1〜40重量%とシリコーンゴムパウダー0.1〜10重量%とを混在させたことを特徴とする耐摩耗性熱可塑性樹脂組成物が記載されている。特許文献2では、シリコーンゴムパウダーは、シリコーンオイル及び/又はシリコーンポリマーなどのシリコーン分が樹脂表面にブリードアウトするのを抑制するために用いられている。
Further,
しかし、このような被膜組成物を摺動部材に適用した場合であっても、オイルがほとんどない境界潤滑状態である上死点や、流体潤滑と境界潤滑との中間状態であり、比較的流体潤滑状態に近い混合状態である下死点近傍では、ピストンなどの摺動部材の速度がゼロとなり、油膜が形成されないため、摩擦が大幅に増大する。 However, even when such a coating composition is applied to a sliding member, it is a top dead center which is a boundary lubrication state in which there is almost no oil, or an intermediate state between fluid lubrication and boundary lubrication, and is relatively fluid. In the vicinity of the bottom dead center, which is a mixed state close to the lubrication state, the speed of the sliding member such as the piston becomes zero, and no oil film is formed, so that the friction is greatly increased.
従って、上死点・下死点において摺動部材の摩擦特性及び耐摩耗性などのフリクションを低減することが求められている。 Therefore, it is required to reduce friction such as friction characteristics and wear resistance of the sliding member at the top dead center and the bottom dead center.
前記のように、従来の被膜組成物を摺動部材に適用した場合、上死点・下死点近傍では摩擦が大幅に増大するため、摩擦特性及び耐摩耗性などのフリクションについては改善の余地がある。 As described above, when the conventional coating composition is applied to the sliding member, the friction greatly increases in the vicinity of the top dead center and the bottom dead center, so there is room for improvement in friction such as friction characteristics and wear resistance. There is.
それ故、本発明は、摩擦特性及び耐摩耗性などのフリクションが改善された摺動部材用被膜組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide a coating composition for a sliding member with improved friction such as friction characteristics and wear resistance.
本発明者らは、前記課題を解決するための手段を種々検討した結果、摺動部材用被膜組成物にシリコーンゴムパウダーを配合し、被膜組成物の膜厚に対するシリコーンゴムパウダーの平均粒径(φ/d)を制御することにより、摩擦特性及び摩耗特性が改善されることを見出し、本発明を完成した。 As a result of various studies on means for solving the above problems, the present inventors formulated silicone rubber powder in the coating composition for sliding members, and obtained an average particle size of the silicone rubber powder with respect to the film thickness of the coating composition ( The inventors have found that by controlling φ / d), friction characteristics and wear characteristics are improved, and the present invention has been completed.
すなわち、本発明の要旨は以下の通りである。
(1)湿式条件で使用される摺動部材用被膜組成物であって、耐熱性樹脂及び3〜30体積%のシリコーンゴムパウダーを含み、被膜組成物の膜厚(d)に対するシリコーンゴムパウダーの平均粒径(φ)の比(φ/d)が0.5〜3である摺動部材用被膜組成物。
(2)潤滑油を含まない(1)の摺動部材用被膜組成物。
(3)耐熱性樹脂が、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルサルフォン樹脂、ポリフェニルサルファイド樹脂、ポリアミド樹脂、エポキシ樹脂及びフェノール樹脂から選択される少なくとも1種である(1)又は(2)の摺動部材用被膜組成物。
(4)ポリテトラフルオロエチレン、二硫化モリブデン及びグラファイトから選択される少なくとも1種の固体潤滑剤をさらに含む(1)〜(3)のいずれかの摺動部材用被膜組成物。
(5)アルミナ及びシリカから選択される少なくとも1種の硬質粒子をさらに含む(1)〜(4)のいずれかの摺動部材用被膜組成物。
(6)被膜組成物の膜厚(d)が5〜20μmである(1)〜(5)のいずれかの摺動部材用被膜組成物。(7)シリコーンゴムパウダーの平均粒径が2.5μm〜60μmである(1)〜(6)のいずれかの摺動部材用被膜組成物。
(8)(1)〜(7)のいずれかの摺動部材用被膜組成物を摺動面に備えた摺動部材。
That is, the gist of the present invention is as follows.
(1) A coating composition for a sliding member used under wet conditions, comprising a heat-resistant resin and 3 to 30% by volume of silicone rubber powder, wherein the silicone rubber powder has a film thickness (d) of the coating composition. A coating composition for a sliding member having an average particle size (φ) ratio (φ / d) of 0.5 to 3.
(2) The coating composition for a sliding member according to (1), which does not contain a lubricating oil.
(3) The heat resistant resin is at least one selected from polyimide resin, polyamideimide resin, polyethersulfone resin, polyphenylsulfide resin, polyamide resin, epoxy resin and phenol resin (1) or (2) A coating composition for a sliding member.
(4) The coating composition for a sliding member according to any one of (1) to (3), further comprising at least one solid lubricant selected from polytetrafluoroethylene, molybdenum disulfide, and graphite.
(5) The coating composition for a sliding member according to any one of (1) to (4), further comprising at least one hard particle selected from alumina and silica.
(6) The coating composition for a sliding member according to any one of (1) to (5), wherein the coating composition has a film thickness (d) of 5 to 20 μm. (7) The coating composition for a sliding member according to any one of (1) to (6), wherein the silicone rubber powder has an average particle size of 2.5 μm to 60 μm.
(8) A sliding member comprising the sliding member coating composition according to any one of (1) to (7) on a sliding surface.
本発明により、摩擦特性及び耐摩耗性に優れた摺動部材用被膜組成物及び摺動面に該被膜組成物を備えた摺動部材を提供することが可能となる。 According to the present invention, it is possible to provide a coating composition for a sliding member having excellent friction characteristics and wear resistance, and a sliding member provided with the coating composition on a sliding surface.
以下、本発明の好ましい実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
1. 摺動部材用被膜組成物
本発明は摺動部材用被膜組成物に関する。本発明の被膜組成物は、潤滑油を用いた湿式条件で使用される摺動部材用の被膜組成物である。
1. Coating composition for sliding member The present invention relates to a coating composition for sliding member. The coating composition of the present invention is a coating composition for a sliding member used under wet conditions using a lubricating oil.
本発明の摺動部材用被膜組成物は、耐熱性樹脂及びシリコーンゴムパウダーを含む。シリコーンゴムパウダーは吸油性成分であり、潤滑油を用いた湿式条件下での摺動部材の摺動中に、シリコーンゴムパウダー分子への潤滑油の吸油と、シリコーンゴムパウダー分子からの潤滑油の排出が可逆的に起こる。原則的には、圧力が作用するとシリコーンゴムパウダー分子に吸油された潤滑油が排出され、圧力がかからなくなると、シリコーンゴムパウダー分子が潤滑油を吸油する。このような効果を有するシリコーンゴムパウダーを含む本発明の被膜組成物は、ピストンなどの摺動部材の速度がゼロとなる上死点・下死点近傍においても、自発的に油膜を形成し、摩擦を低減することができる。また、本発明の摺動部材用被膜組成物は、好ましくは、シリコーンオイルなどの潤滑油を含まない。ここで、潤滑油を含まない摺動部材用被膜組成物とは、湿式条件で使用される前の組成物が潤滑油を含まないことを意味し、湿式条件下で摺動した際、摺動にともない潤滑油を吸油した組成物は、本発明の被膜組成物に含まれる。被膜組成物が、シリコーンオイルなどの潤滑油を含まないことによって、塗膜強度を高めることができる。 The coating composition for a sliding member of the present invention contains a heat resistant resin and silicone rubber powder. Silicone rubber powder is an oil-absorbing component, and when the sliding member slides under wet conditions using lubricating oil, the lubricating oil is absorbed into the silicone rubber powder molecules and the lubricating oil from the silicone rubber powder molecules. Discharge occurs reversibly. In principle, when the pressure is applied, the lubricating oil absorbed by the silicone rubber powder molecules is discharged, and when the pressure is no longer applied, the silicone rubber powder molecules absorb the lubricating oil. The coating composition of the present invention containing the silicone rubber powder having such an effect spontaneously forms an oil film even in the vicinity of the top dead center / bottom dead center where the speed of the sliding member such as the piston becomes zero, Friction can be reduced. Moreover, the coating composition for a sliding member of the present invention preferably does not contain a lubricating oil such as silicone oil. Here, the coating composition for sliding members that does not contain lubricating oil means that the composition before being used under wet conditions does not contain lubricating oil. Accordingly, the composition that has absorbed the lubricating oil is included in the coating composition of the present invention. Since the coating composition does not contain a lubricating oil such as silicone oil, the coating strength can be increased.
本発明の摺動部材用被膜組成物に用いられる耐熱性樹脂は、特に限定されずに、100℃以上、好ましくは150℃以上の熱変形温度を有するものである。耐熱性樹脂の例としては、特に限定されずに、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリエーテルサルフォン樹脂、ポリフェニルサルファイド樹脂、ポリアミド樹脂、アルキド樹脂、エポキシ樹脂、アミノ樹脂、ポリアミノアミド樹脂、不飽和ポリエステル樹脂、フェノール樹脂、キシレン樹脂、ビニルエステル樹脂、フラン樹脂、シリコーン樹脂及び全芳香族ポリエステル樹脂などを挙げることができるが、接着性、耐薬品性、強度などの観点から、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルサルフォン樹脂、ポリフェニルサルファイド樹脂、ポリアミド樹脂、エポキシ樹脂及びフェノール樹脂が好ましく、被膜を形成する際の作業性と摩擦による発熱に対する耐熱性の観点からポリアミドイミド樹脂が更に好ましい。これらの耐熱性樹脂は、1種のみを単独で使用してもよく、2種以上を混合使用してもよい。 The heat resistant resin used in the coating composition for a sliding member of the present invention is not particularly limited and has a heat distortion temperature of 100 ° C. or higher, preferably 150 ° C. or higher. Examples of the heat-resistant resin are not particularly limited, but are not limited to polyimide resin, polyamideimide resin, polyetherimide resin, polyethersulfone resin, polyphenylsulfide resin, polyamide resin, alkyd resin, epoxy resin, amino resin, polyamino Amide resin, unsaturated polyester resin, phenol resin, xylene resin, vinyl ester resin, furan resin, silicone resin and wholly aromatic polyester resin can be mentioned, but from the viewpoint of adhesiveness, chemical resistance, strength, etc. Polyimide resin, polyamideimide resin, polyethersulfone resin, polyphenylsulfide resin, polyamide resin, epoxy resin and phenol resin are preferable. Polyamide resin is used from the viewpoint of workability during film formation and heat resistance against heat generated by friction. Resin is more preferable. These heat resistant resins may be used alone or in combination of two or more.
組成物中の耐熱性樹脂の含有量は、被膜組成物の強度を維持する観点から、被膜組成物に対して好ましくは40体積%〜97体積%、更に好ましくは60体積%〜90体積%、特に好ましくは70体積%〜85体積%である。 The content of the heat resistant resin in the composition is preferably 40% by volume to 97% by volume, more preferably 60% by volume to 90% by volume, with respect to the coating composition, from the viewpoint of maintaining the strength of the coating composition. Most preferably, it is 70 volume%-85 volume%.
本発明の摺動部材用被膜組成物は、シリコーンゴムパウダーを3〜30体積%、好ましくは5〜20体積%含む。組成物中のシリコーンゴムパウダーの含有量がこの範囲であると、優れた摩擦低減効果が得られ、耐摩耗性を維持することもできる。 The coating composition for a sliding member of the present invention contains 3 to 30% by volume, preferably 5 to 20% by volume of silicone rubber powder. When the content of the silicone rubber powder in the composition is within this range, an excellent friction reducing effect can be obtained and the wear resistance can be maintained.
本発明の摺動部材用被膜組成物において、被膜組成物の膜厚(d)に対するシリコーンゴムパウダーの平均粒径(φ)の比(φ/d)は0.5〜3であり、好ましくは0.8〜1.2である。φ/dが0.5未満であると、シリコーンゴムパウダーが摺動面に表れるまでに時間がかかり、また、摺動面におけるシリコーンゴムパウダーの面積率が小さいため、充分な摩擦低減効果が得られない。また、φ/dが3より大きい場合には、シリコーンゴムパウダーが、摺動中に被膜組成物から脱離し易いため、充分な摩擦低減効果が得られない。 In the coating composition for a sliding member of the present invention, the ratio (φ / d) of the average particle diameter (φ) of the silicone rubber powder to the film thickness (d) of the coating composition is 0.5 to 3, preferably 0.8 to 1.2. When φ / d is less than 0.5, it takes time until the silicone rubber powder appears on the sliding surface, and the area ratio of the silicone rubber powder on the sliding surface is small, so a sufficient friction reducing effect cannot be obtained. . When φ / d is larger than 3, the silicone rubber powder is easily detached from the coating composition during sliding, so that a sufficient friction reducing effect cannot be obtained.
シリコーンゴムパウダーの平均粒径は、前記の特定のφ/dの値を満たすものであれば特に限定されないが、充分な摩擦低減効果を得るためには、好ましくは2.5μm〜60μm、更に好ましくは5μm〜20μmである。平均粒径はレーザー回折散乱法によって決定することができる。 The average particle size of the silicone rubber powder is not particularly limited as long as it satisfies the above specific φ / d value, but in order to obtain a sufficient friction reducing effect, preferably 2.5 μm to 60 μm, more preferably 5 μm to 20 μm. The average particle diameter can be determined by a laser diffraction scattering method.
本発明の摺動部材用被膜組成物の膜厚は、好ましくは5〜20μmである。被膜組成物の膜厚がこの範囲であると、例えば、ピストンスカートに用いて充分なフリクション低減効果を得ることができる。 The film thickness of the coating composition for a sliding member of the present invention is preferably 5 to 20 μm. When the film thickness of the coating composition is within this range, for example, a sufficient friction reducing effect can be obtained by using it for a piston skirt.
本発明の摺動部材用被膜組成物は、摩擦特性を向上させるために、1種以上の固体潤滑剤をさらに含むことができる。本発明の組成物に用いることができる固体潤滑剤としては、特に限定されずに、例えば、ポリテトラフルオロチエチレン(PTFE)、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン-エチレン共重合体、ポリビニリデンフルオライド及びポリクロロトリフルオロエチレンなどのフッ素化合物、二硫化モリブデン(MoS2)及び二硫化タングステン(WS2)などの硫化物、グラファイト(黒鉛)、フッ化グラファイト、窒化硼素、マイカなどの層状鱗片状物質、鉛、亜鉛、銅などの軟質金属、メラミンシアヌレートなどが挙げられるが、広い温度範囲における高い自己摺動性の維持の観点から、ポリテトラフルオロエチレン、二硫化モリブデン及びグラファイトが好ましい。これらは1種のみを単独で使用しても良く、2種以上を併用してもよい。 The coating composition for a sliding member of the present invention can further contain one or more solid lubricants in order to improve the friction characteristics. The solid lubricant that can be used in the composition of the present invention is not particularly limited. For example, polytetrafluorothiethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexa Fluoropropylene copolymers, tetrafluoroethylene-ethylene copolymers, fluorine compounds such as polyvinylidene fluoride and polychlorotrifluoroethylene, sulfides such as molybdenum disulfide (MoS 2 ) and tungsten disulfide (WS 2 ), Examples include layered scaly substances such as graphite (graphite), graphite fluoride, boron nitride, and mica, soft metals such as lead, zinc, and copper, and melamine cyanurate, but maintain high self-sliding properties over a wide temperature range. From the viewpoint of polytetrafluoroethylene, molybdenum disulfide and Rafaito is preferable. These may be used alone or in combination of two or more.
組成物中の1種以上の固体潤滑剤の含有量は、特に限定されずに用いる固体潤滑剤の種類に応じて選択することができ、例えば、ポリテトラフルオロエチレンは20体積%以下の量で、二硫化モリブデンは30体積%以下の量で、グラファイトは20体積%以下の量で組成物に含まれる。固体潤滑剤をこの範囲の量で用いると、充分な摩擦低減効果が得られ、耐焼付特性に影響を及ぼさず、さらに、被膜が摺動部材の基材から剥離することなく充分な強度を保つことができる。 The content of one or more solid lubricants in the composition is not particularly limited and can be selected according to the type of solid lubricant used, for example, polytetrafluoroethylene is in an amount of 20% by volume or less. Molybdenum disulfide is contained in the composition in an amount of 30% by volume or less, and graphite is contained in an amount of 20% by volume or less. When the solid lubricant is used in an amount within this range, a sufficient friction reducing effect is obtained, the seizure resistance is not affected, and the coating does not peel off from the base material of the sliding member and maintains a sufficient strength. be able to.
固体潤滑剤の平均粒径は、特に限定されずに、被膜の膜厚に応じて選択することができるが、好ましくは0.1μm〜30μmである。平均粒径がこの範囲であると、例えば、膜厚が5μm〜20μmである場合に、固体潤滑剤が被膜から脱離せず、摩擦係数に悪影響を及ぼさないためである。 The average particle size of the solid lubricant is not particularly limited and can be selected according to the film thickness of the coating, but is preferably 0.1 μm to 30 μm. This is because when the average particle diameter is within this range, for example, when the film thickness is 5 μm to 20 μm, the solid lubricant is not detached from the coating and does not adversely affect the coefficient of friction.
また、本発明の摺動部材用被膜組成物は、耐摩耗性及び耐焼付特性を向上させるために、1種以上の硬質粒子をさらに含むことができる。本発明の組成物に用いることができる硬質粒子としては、特に限定されずに、アルミナ(酸化アルミニウム)(Al2O3)、水酸化アルミニウム、アルミナホワイト、シリカアルミナ、ジルコニア、炭化タングステン、炭化チタン、炭化ケイ素、二酸化チタン、酸化鉄、長石、軽石、正長石、イリジウム、石英、シリカ、酸化ベリリウム、酸化ジルコニウム、クロム、ボロンカーバイト、タングステンカーバイト、シリコーンカーバイト、ダイヤモンドなどが挙げられるが、アルミナ及びシリカが好ましい。硬質粒子は、1種のみを単独で使用してもよいし、2種以上を併用してもよい。 In addition, the coating composition for a sliding member of the present invention can further contain one or more kinds of hard particles in order to improve wear resistance and seizure resistance. The hard particles that can be used in the composition of the present invention are not particularly limited, but alumina (aluminum oxide) (Al 2 O 3 ), aluminum hydroxide, alumina white, silica alumina, zirconia, tungsten carbide, titanium carbide , Silicon carbide, titanium dioxide, iron oxide, feldspar, pumice, orthoclase, iridium, quartz, silica, beryllium oxide, zirconium oxide, chromium, boron carbide, tungsten carbide, silicone carbide, diamond, etc. Alumina and silica are preferred. Only one hard particle may be used alone, or two or more hard particles may be used in combination.
組成物中の1種以上の硬質粒子の含有量は、樹脂コーティングの強度を保つことができる量であれば特に限定されず、例えば、アルミナは10体積%以下の量で組成物に含まれる。 The content of the one or more hard particles in the composition is not particularly limited as long as the strength of the resin coating can be maintained. For example, alumina is contained in the composition in an amount of 10% by volume or less.
硬質粒子の平均粒径は、特に限定されずに、被膜の膜厚に応じて選択することができるが、好ましくは0.1μm〜20μmである。平均粒径がこの範囲であると、例えば、膜厚が5μm〜20μmである場合に、硬質粒子が被膜から脱離せず、摩擦係数に悪影響を及ぼさないためである。 The average particle diameter of the hard particles is not particularly limited and can be selected according to the film thickness of the coating, but is preferably 0.1 μm to 20 μm. This is because when the average particle diameter is within this range, for example, when the film thickness is 5 μm to 20 μm, the hard particles are not detached from the coating, and the coefficient of friction is not adversely affected.
本発明の被膜組成物は、前記の成分以外の他の一般的な添加剤を含むこともできる。添加剤としては、固体潤滑剤や硬質粒子を分散させるための分散剤、硬質粒子への親和性の向上や接着性向上を補助するシランカップリング剤、表面張力をコントロールするレベリング剤や界面活性剤、チクソトロピック特性をコントロールする増粘剤、顔料などが挙げられる。顔料としては、カーボンブラック、酸化チタン、酸化鉄などに代表される着色顔料、錆の発生を抑制する防錆顔料、被膜の性状をコントロールする体質顔料などが挙げられる。 The coating composition of this invention can also contain other general additives other than the said component. Additives include solid lubricants and dispersants for dispersing hard particles, silane coupling agents that help improve affinity and adhesion to hard particles, leveling agents and surfactants that control surface tension And thickeners and pigments for controlling thixotropic properties. Examples of the pigment include color pigments typified by carbon black, titanium oxide, and iron oxide, rust preventive pigments that suppress the generation of rust, and extender pigments that control the properties of the film.
本発明の被膜組成物は、前記の耐熱性樹脂、シリコーンゴムパウダー、並びに必要に応じて固体潤滑剤、硬質粒子及び他の一般的な添加剤を含む混合物を調製し、この混合物を摺動部材の基材にコーティングすることによって得ることができる。 The coating composition of the present invention prepares a mixture containing the above heat-resistant resin, silicone rubber powder, and if necessary, a solid lubricant, hard particles, and other general additives, and this mixture is used as a sliding member. Can be obtained by coating the substrate.
本発明において、摺動部材とは摺動部分を有する機械部品を意味し、具体的には、湿式クラッチ、エンジンのピストン、ギヤ、スプライン、軸受、ワッシャー、動弁系部品などが挙げられる。本発明の摺動部材は、潤滑油を用いた湿式条件で摺動させることを意図したものである。 In the present invention, the sliding member means a mechanical part having a sliding part, and specifically includes a wet clutch, an engine piston, a gear, a spline, a bearing, a washer, and a valve operating system part. The sliding member of the present invention is intended to slide under wet conditions using lubricating oil.
本発明の摺動部材の基材は、各種装置の摺動部品であれば形状などに特に限定はなく、金属系基材、セラミックス系基材、樹脂系基材などいずれであってもよいが、金属製であることが好ましい。基材を構成する金属としては、鋳鉄、鋼、アルミニウムに加えてCu、Mg、Znなどを含むアルミニウム合金、銅に加えてZn、Al、Snなどを含む銅合金などが好ましい。 The base material of the sliding member of the present invention is not particularly limited in shape as long as it is a sliding part of various apparatuses, and may be any of a metal base material, a ceramic base material, a resin base material, etc. It is preferably made of metal. The metal constituting the substrate is preferably an aluminum alloy containing Cu, Mg, Zn or the like in addition to cast iron, steel or aluminum, or a copper alloy containing Zn, Al or Sn in addition to copper.
基材にコーティングされる混合物は、前記の成分の他に、耐熱性樹脂を溶解するための有機溶剤を含むことができる。本発明に用いる有機溶剤は、特に限定されずに耐熱性樹脂の種類に応じて選択される。例えば、耐熱性樹脂としてポリアミドイミド樹脂を用いる場合には、N-メチル-2-ピロリドン(NMP)、N-エチルピロリドン(NEP)、1,3-ジメチル-2-イミダゾリジノン(DMI)及びγ-ブチロラクトンなどを用いることができる。また、エポキシ樹脂を用いる場合には、メチルエチルケトン及びトルエンなどを用いることができる。 The mixture coated on the substrate may contain an organic solvent for dissolving the heat resistant resin, in addition to the above components. The organic solvent used for this invention is not specifically limited, According to the kind of heat resistant resin, it selects. For example, when a polyamideimide resin is used as the heat resistant resin, N-methyl-2-pyrrolidone (NMP), N-ethylpyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI) and γ -Butyrolactone can be used. Moreover, when using an epoxy resin, methyl ethyl ketone, toluene, etc. can be used.
混合物は、例えば、耐熱性樹脂を有機溶剤に溶解した溶解液を準備し、この溶解液にシリコーンゴムパウダー、並びに必要に応じて固体潤滑剤、硬質粒子及び他の一般的な添加剤などの成分を加え、混合することによって得ることができる。 The mixture is prepared by, for example, preparing a solution obtained by dissolving a heat-resistant resin in an organic solvent, and adding components such as a silicone rubber powder, solid lubricant, hard particles, and other general additives to the solution. And can be obtained by mixing.
混合物の基材へのコーティング方法としては、特に限定されずに、スプレーコーティングなどの公知のコーティング方法を用いることができ、その後、耐熱性樹脂を乾燥、硬化させることができる条件で焼成することにより、被膜組成物を得ることができる。焼成条件は、特に限定されずに、例えば、100℃〜370℃の温度で30分〜3時間である。 The coating method of the mixture on the base material is not particularly limited, and a known coating method such as spray coating can be used. Thereafter, the heat-resistant resin is baked under conditions capable of drying and curing. A coating composition can be obtained. The firing conditions are not particularly limited, and are, for example, 30 minutes to 3 hours at a temperature of 100 ° C. to 370 ° C.
2. 摺動部材
本発明は、潤滑油の存在下で摺動される摺動面に摺動部材用被膜組成物を備えた摺動部材にも関する。本発明の摺動部材は、摺動面の被膜組成物がシリコーンゴムパウダーを含み、被膜組成物の膜厚に対するシリコーンゴムパウダーの平均粒径(φ/d)が特定の範囲であることを特徴とし、これにより、優れた摩擦特性及び耐摩耗特性を示す。
2. Sliding member The present invention also relates to a sliding member provided with a coating composition for a sliding member on a sliding surface that is slid in the presence of lubricating oil. The sliding member of the present invention is characterized in that the coating composition on the sliding surface contains silicone rubber powder, and the average particle diameter (φ / d) of the silicone rubber powder with respect to the film thickness of the coating composition is in a specific range. Thus, excellent friction characteristics and wear resistance characteristics are exhibited.
本発明の摺動部材に用いる潤滑油としては、特に限定されずに、例えば、ATF(オートマチック・トランスミッションオイル)、CVTF(無段変速機オイル）、ギヤ油などの駆動系油、ガソリン、軽油などの燃料油、エンジン油などが挙げられる。 The lubricating oil used for the sliding member of the present invention is not particularly limited. For example, ATF (automatic transmission oil), CVTF (continuously variable transmission oil), drive oil such as gear oil, gasoline, light oil, etc. Fuel oil, engine oil and the like.
本発明の摺動部材は、ピストン、軸受及びワッシャーなどであることができる。 The sliding member of the present invention can be a piston, a bearing, a washer or the like.
以下、実施例を用いて本発明をさらに具体的に説明する。但し、本発明の技術的範囲はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the technical scope of the present invention is not limited to these examples.
実施例1
1. テストピースの作成
80体積%のポリアミドイミド樹脂(HPC-5000-30:日立化成工業株式会社製)をN-メチル-2-ピロリドン(NMP)に溶解した。得られたポリアミドイミド樹脂の溶解液に3体積%のシリコーンゴムパウダー(KMP-598:信越化学工業社製:平均粒径13μm)を加え、ニーダーで1時間混練を行い、混合物を得た。
Example 1
1. Creating a test piece
80% by volume of polyamideimide resin (HPC-5000-30: manufactured by Hitachi Chemical Co., Ltd.) was dissolved in N-methyl-2-pyrrolidone (NMP). 3% by volume of silicone rubber powder (KMP-598: manufactured by Shin-Etsu Chemical Co., Ltd .: average particle size: 13 μm) was added to the obtained solution of polyamideimide resin, and kneaded for 1 hour to obtain a mixture.
得られた混合物を鋳造アルミAC8Aよりなるプレート形状の基材表面にスプレーコーティングを行い、180℃で90分間焼成してN-メチル-2-ピロリドンを揮発させることにより、膜厚10μm、φ/d=1.3の被膜組成物が形成した摩擦特性評価用のテストピースを作製した。 The obtained mixture is spray-coated on the surface of a plate-shaped substrate made of cast aluminum AC8A, and baked at 180 ° C. for 90 minutes to volatilize N-methyl-2-pyrrolidone, resulting in a film thickness of 10 μm, φ / d A test piece for evaluating frictional characteristics formed with a coating composition of = 1.3 was prepared.
また、得られた被膜組成物を鋳造アルミAC8Aよりなるブロック形状の基材表面に、スプレーコーティングを行い、180℃で90分間焼成してN-メチル-2-ピロリドンを揮発させることにより、膜厚10μmの被膜組成物が形成した摩耗特性評価用のブロックテストピースを作製した。 The resulting coating composition was spray coated on the surface of a block-shaped substrate made of cast aluminum AC8A, and baked at 180 ° C. for 90 minutes to volatilize N-methyl-2-pyrrolidone. A block test piece for evaluating wear characteristics formed of a 10 μm coating composition was prepared.
2. 摩擦特性評価
図1に示すように、直径10mmのSUJ2よりなる軸受球を平板テストピース上面に押しつけて、摩擦特性を評価した。エンジン油をプレート上(58×38mm)に1mg均一に滴下して、荷重10N、摺動速度2Hz(最大0.1m/s)にて50往復揺動試験における平均摩擦係数を評価した。この試験は油量が微量であり、貧潤滑条件下での試験であるため、ピストン挙動における上下死点付近での潤滑状態を再現した試験であるといえる。
2. Evaluation of friction characteristics As shown in Fig. 1, a bearing ball made of SUJ2 with a diameter of 10 mm was pressed against the upper surface of a flat test piece to evaluate the friction characteristics. 1 mg of engine oil was uniformly dropped on the plate (58 x 38 mm), and the average friction coefficient in a 50 reciprocating rocking test was evaluated at a load of 10 N and a sliding speed of 2 Hz (maximum 0.1 m / s). Since this test is a test with a small amount of oil and under poor lubrication conditions, it can be said that the test reproduced the lubrication state near the top and bottom dead center in the piston behavior.
3. 摩耗特性評価
図2に示すように、ブロックテストピースを回転するねずみ鋳鉄FC250よりなる相手材円筒テストピースの側面に押し付けて、摩耗特性を評価した。エンジン油(80℃)においてならし運転後、試験面圧30MPaにて一定時間の摩耗試験を行った後の被膜の摩耗深さを測定して、摩耗特性を評価した。
3. Evaluation of wear characteristics As shown in Fig. 2, the wear characteristics were evaluated by pressing the block test piece against the side of a mating cylindrical test piece made of gray cast iron FC250. After running-in with engine oil (80 ° C.), the wear depth was evaluated by measuring the wear depth of the coating after performing a wear test for a fixed time at a test surface pressure of 30 MPa.
実施例2〜5
シリコーンゴムパウダーの含有量を5、10、20、30体積%に変え、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例1と同様にした。実施例2〜5の被膜組成物の組成は表1に示した。
Examples 2-5
The same procedure as in Example 1 was conducted, except that the content of the silicone rubber powder was changed to 5, 10, 20, and 30% by volume, and the amount of the polyamideimide resin was changed accordingly. The compositions of the coating compositions of Examples 2 to 5 are shown in Table 1.
比較例1
従来の被膜組成物として、有機溶剤としてN-メチル-2-ピロリドン(NMP)を用い、86体積%のポリアミドイミド樹脂、7体積%の二硫化モリブデン(MoS2)、2体積%のグラファイト及び5体積%のテフロン(登録商標)(ポリテトラフルオロエチレン)を含む組成物を用いた。この被膜組成物は、特開平7-97517号公報に記載の通りに調製した。表1に、比較例1の被膜組成物の組成を示した。
Comparative Example 1
As a conventional coating composition, using N-methyl-2-pyrrolidone (NMP) as an organic solvent, 86% by volume polyamideimide resin, 7% by volume molybdenum disulfide (MoS 2 ), 2% by volume graphite and 5% A composition containing% by volume of Teflon (polytetrafluoroethylene) was used. This coating composition was prepared as described in JP-A-7-97517. Table 1 shows the composition of the coating composition of Comparative Example 1.
比較例2、3
シリコーンゴムパウダーの含有量を1、50体積%に変え、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例1と同様にした。比較例2、3の被膜組成物の組成は表１に示した。
Comparative Examples 2 and 3
Example 1 was repeated except that the content of the silicone rubber powder was changed to 1, 50% by volume and the amount of the polyamideimide resin was changed correspondingly. The compositions of the coating compositions of Comparative Examples 2 and 3 are shown in Table 1.
実施例1〜5及び比較例1〜3で得られた摩擦係数を図3に示した。実施例1〜5及び比較例3では、比較例1及び2に対して摩擦係数が著しく低減した。実施例1〜5を比較例1と比較すると、吸油性成分であるシリコーンゴムパウダーを添加することにより、摩擦係数が大幅に低減することが示された。また、シリコーンゴムパウダーの含有量の増加にともない、摩擦係数の低減が認められるが、その含有量が30体積%以上になると、摩擦係数の値はほぼ一定値(0.02〜0.03)に漸近していた。シリコーンゴムパウダーによる摩擦低減効果は絶大であり、例えば、シリコーンゴムパウダーを20体積%配合することにより(実施例4)、比較例1に対して約80%の摩擦低減効果が得られた。 The friction coefficients obtained in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in FIG. In Examples 1 to 5 and Comparative Example 3, the friction coefficient was remarkably reduced as compared with Comparative Examples 1 and 2. When Examples 1 to 5 were compared with Comparative Example 1, it was shown that the friction coefficient was significantly reduced by adding silicone rubber powder, which is an oil-absorbing component. In addition, as the content of silicone rubber powder increases, the friction coefficient decreases, but when the content exceeds 30% by volume, the value of the friction coefficient gradually approaches a constant value (0.02 to 0.03). It was. The friction reducing effect of the silicone rubber powder is enormous. For example, by adding 20% by volume of the silicone rubber powder (Example 4), a friction reducing effect of about 80% with respect to Comparative Example 1 was obtained.
また、実施例1〜5及び比較例1〜3の摩耗量をグラフに表したものを図4に示した。シリコーンゴムパウダーの含有量の増加にともなって摩耗量は増加し、シリコーンゴムパウダーが50体積%の場合(比較例3)、摩耗量は約14μmとなり、材料の信頼性を保つことができる下限の約10μmよりも摩耗量が大きかった。 Further, FIG. 4 shows graphs of the wear amounts of Examples 1 to 5 and Comparative Examples 1 to 3. As the content of silicone rubber powder increases, the amount of wear increases.When the amount of silicone rubber powder is 50% by volume (Comparative Example 3), the amount of wear is about 14 μm, which is the lower limit that can maintain the reliability of the material. The amount of wear was greater than about 10 μm.
図3及び図4より、被膜組成物中のシリコーンゴムパウダーの含有量は、3〜30体積%であることが好ましく、5〜20体積%であることが更に好ましい。 From FIG. 3 and FIG. 4, the content of the silicone rubber powder in the coating composition is preferably 3 to 30% by volume, more preferably 5 to 20% by volume.
また、実施例1〜5の被膜組成物の油吸収量及び材料の油吸収量は、比較例1のものよりも優れていた。 Moreover, the oil absorption amount of the coating compositions of Examples 1 to 5 and the oil absorption amount of the materials were superior to those of Comparative Example 1.
実施例6
ポリアミドイミド樹脂をエポキシ樹脂(1007:三菱化学株式会社製)（ただし、硬化剤としてアミノ樹脂（J-820-60：DIC株式会社製）を使用）に代えた以外は実施例4と同様にした。表2に、実施例6の被膜組成物の組成を示した。
Example 6
Example 4 was repeated except that the polyamideimide resin was replaced with an epoxy resin (1007: manufactured by Mitsubishi Chemical Corporation) (however, an amino resin (J-820-60: manufactured by DIC Corporation) was used as a curing agent). . Table 2 shows the composition of the coating composition of Example 6.
比較例4〜9
シリコーンゴムパウダーを用いずに(比較例4)、又はシリコーンゴムパウダーに代えて、二硫化モリブデン(MoS2)(比較例5)、グラファイト(比較例6)、テフロン(登録商標)(比較例7)、シリコーンレジン(比較例8)、ナイロン(比較例9)を用いる以外は実施例4と同様にした。表2に、比較例4〜9の被膜組成物の組成を示した。
Comparative Examples 4-9
Without using silicone rubber powder (Comparative Example 4), or instead of silicone rubber powder, molybdenum disulfide (MoS 2 ) (Comparative Example 5), graphite (Comparative Example 6), Teflon (registered trademark) (Comparative Example 7) ), Silicone resin (Comparative Example 8), and nylon (Comparative Example 9). Table 2 shows the compositions of the coating compositions of Comparative Examples 4-9.
実施例6及び比較例4〜9で得られた摩擦係数を図5に示した。実施例6は、実施例4と同程度の摩擦係数を示し、本発明の耐熱性樹脂として、ポリアミドイミド樹脂と同様にエポキシ樹脂を用いることができた。また、シリコーンゴムパウダーを用いない場合(比較例4)や、シリコーンゴムパウダーに代えて吸油特性の極めて低い固体潤滑剤である二硫化モリブデン(MoS2)(比較例5)、グラファイト(比較例6)や、同様に吸油特性の極めて低い樹脂であるシリコーンレジン(比較例8)、ナイロン(比較例9)を用いた場合と比較して、シリコーンゴムパウダーを用いた実施例4、6では優れた摩擦低減効果が示された。 The friction coefficients obtained in Example 6 and Comparative Examples 4 to 9 are shown in FIG. Example 6 showed the same coefficient of friction as Example 4, and an epoxy resin could be used as the heat-resistant resin of the present invention in the same manner as the polyamideimide resin. Also, when no silicone rubber powder is used (Comparative Example 4), molybdenum disulfide (MoS 2 ) (Comparative Example 5), graphite (Comparative Example 6), which is a solid lubricant with extremely low oil absorption characteristics instead of silicone rubber powder ) And silicone resins (Comparative Example 8) and nylon (Comparative Example 9), which are also resins with extremely low oil absorption properties, are superior in Examples 4 and 6 using silicone rubber powder. A friction reducing effect was shown.
また、シリコーンゴムパウダーを用いた実施例4、6の被膜組成物の油吸収量及び材料の油吸収量は、比較例4〜9のものよりも優れていた。 Moreover, the oil absorption amount of the coating compositions of Examples 4 and 6 using the silicone rubber powder and the oil absorption amount of the material were superior to those of Comparative Examples 4 to 9.
[固体潤滑剤及び硬質粒子の配合量の摩擦係数、焼付特性及び剥離特性への影響]
実施例7〜20では、固体潤滑剤及び硬質粒子の配合量の摩擦係数への影響を評価した。実施例7〜9では、固体潤滑剤として二硫化モリブデン(MoS2)をそれぞれ所定の量で用い、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例4と同様にした。実施例10〜12では、固体潤滑剤としてグラファイトをそれぞれ所定の量で用い、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例4と同様にした。実施例13〜15では、固体潤滑剤としてテフロン(登録商標)(ポリテトラフルオロエチレン)をそれぞれ所定の量で用い、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例4と同様にした。実施例16、17では、固体潤滑剤として二硫化モリブデン(MoS2)、グラファイト及びテフロン(登録商標)をそれぞれ所定の量で用い、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例4と同様にした。実施例18〜20では、固体潤滑剤として二硫化モリブデン(MoS2)、グラファイト及びテフロン(登録商標)をそれぞれ所定の量で用い、硬質粒子としてアルミナ(Al2O3)をそれぞれ所定の量で用い、それに対応してポリアミドイミド樹脂の量を変えた以外は実施例4と同様にした。表3に、実施例7〜20の樹脂組成物の組成を示した。
[Effects of blending amount of solid lubricant and hard particles on friction coefficient, seizure characteristics, and peeling characteristics]
In Examples 7 to 20, the influence of the blending amount of the solid lubricant and hard particles on the friction coefficient was evaluated. Examples 7 to 9 were the same as Example 4 except that molybdenum disulfide (MoS 2 ) was used in a predetermined amount as a solid lubricant, and the amount of polyamideimide resin was changed accordingly. Examples 10 to 12 were the same as Example 4 except that graphite was used as a solid lubricant in predetermined amounts, and the amount of polyamideimide resin was changed accordingly. In Examples 13 to 15, Teflon (registered trademark) (polytetrafluoroethylene) was used as a solid lubricant in a predetermined amount, and the amount of polyamideimide resin was changed correspondingly, as in Example 4. did. In Examples 16 and 17, molybdenum disulfide (MoS 2 ), graphite, and Teflon (registered trademark) were used as solid lubricants in predetermined amounts, respectively, except that the amount of polyamideimide resin was changed correspondingly. Same as 4. In Examples 18 to 20, molybdenum disulfide (MoS 2 ), graphite, and Teflon (registered trademark) are used in predetermined amounts as solid lubricants, and alumina (Al 2 O 3 ) is used as hard particles in predetermined amounts. The procedure was the same as in Example 4 except that the amount of the polyamideimide resin was changed correspondingly. Table 3 shows the compositions of the resin compositions of Examples 7 to 20.
実施例7〜20で得られた摩擦係数及び焼付特性をそれぞれ図6及び7に示し、剥離特性の評価結果を表3に示した。焼付特性及び剥離特性の評価は以下の通り行った。 The friction coefficient and the seizure characteristics obtained in Examples 7 to 20 are shown in FIGS. 6 and 7, respectively, and the evaluation results of the peeling characteristics are shown in Table 3. Evaluation of seizure characteristics and peeling characteristics was performed as follows.
〈焼付特性の評価〉
焼付特性を評価するためのテストピースとしては、摩擦特性評価用のテストピースを使用した。図8に示すように、回転する平板テストピースをねずみ鋳鉄FC250よりなる相手材の円筒テストピースの端面に押しつけて、焼付特性を評価した。試験条件は、エンジン油中(80℃)においてならし運転後、試験荷重をステップアップさせた時の試験面圧20MPa時の摩擦係数にて摩擦特性を評価し、さらに試験荷重をステップアップさせ、平板テストピースの樹脂組成物の被膜が摩滅、又は剥離したときに相手剤と基材とが直接接触し、トルクが急上昇する荷重(焼付荷重)にて焼付特性を評価した。
<Evaluation of seizure characteristics>
As a test piece for evaluating seizure characteristics, a test piece for evaluating friction characteristics was used. As shown in FIG. 8, the rotating flat plate test piece was pressed against the end face of the mating cylindrical test piece made of gray cast iron FC250 to evaluate the seizure characteristics. The test conditions were as follows: After the leveling operation in engine oil (80 ° C), the friction characteristics were evaluated with the friction coefficient at the test surface pressure of 20 MPa when the test load was stepped up, and the test load was further stepped up. When the coating of the resin composition of the flat plate test piece was worn away or peeled off, the counterpart and the base material were in direct contact with each other, and the seizure characteristics were evaluated by a load at which the torque increased rapidly (baking load).
〈剥離特性の評価〉
剥離特性を評価するためのテストピースは、摩擦特性評価用のテストピースと同様にして作製した。図9に示すように、直径1/8インチのSUJ2よりなる軸受球を平板テストピース上面に押しつけて、剥離特性を評価した。試験条件は、エンジン油を平板上に均一に塗布した状態で、試験荷重を0.5〜10Nに徐々にスイープ増加させていき（1ストローク中に変動）、速度15mm/秒で200回摺動させ、試験後に被膜が残存している最大荷重を剥離荷重として計測し、比較評価した。
<Evaluation of peeling properties>
A test piece for evaluating the peeling characteristics was produced in the same manner as the test piece for evaluating the friction characteristics. As shown in FIG. 9, a bearing ball made of SUJ2 having a diameter of 1/8 inch was pressed against the upper surface of a flat plate test piece to evaluate the peeling characteristics. The test conditions were as follows: engine oil was evenly applied on a flat plate and the test load was gradually increased from 0.5 to 10N by sweeping (fluctuated during one stroke), sliding 200 times at a speed of 15mm / sec. The maximum load in which the film remained after the test was measured as a peel load and subjected to comparative evaluation.
実施例7〜20のいずれにおいても、シリコーンゴムパウダーが被膜組成物に配合されているため、比較例1と比較すると摩擦係数は大幅に低減した。また、実施例7〜20の焼付特性について、いずれも焼付面圧は20MPa以上であり、摺動部材としての使用に問題無いと考えられる。しかし、剥離特性の結果から、固体潤滑剤及び硬質粒子の配合量が増加すると、被膜の脆弱化が進行し、より剥離しやすい被膜となった。以上の結果より、固体潤滑剤としてのポリテトラフルオロエチレンは20体積%以下の量で、二硫化モリブデンは30体積%以下の量で、グラファイトは20体積%以下の量で組成物に含まれることが好ましく、また、硬質粒子としてのアルミナは10体積%以下の量で組成物に含まれることが好ましい。 In any of Examples 7 to 20, since the silicone rubber powder was blended in the coating composition, the friction coefficient was significantly reduced as compared with Comparative Example 1. Further, regarding the seizure characteristics of Examples 7 to 20, the seizure surface pressure is 20 MPa or more, and it is considered that there is no problem in use as a sliding member. However, from the results of the peeling characteristics, when the blending amount of the solid lubricant and the hard particles is increased, the coating becomes more brittle and the coating is more easily peeled off. From the above results, polytetrafluoroethylene as a solid lubricant is contained in the composition in an amount of 20% by volume or less, molybdenum disulfide in an amount of 30% by volume or less, and graphite in an amount of 20% by volume or less. In addition, it is preferable that alumina as hard particles is contained in the composition in an amount of 10% by volume or less.
[φ/dの摩擦係数への影響]
実施例4、21、22及び比較例10〜14では、φ/dの摩擦係数への影響を評価した。実施例21、22及び比較例10〜14は、被膜組成物の膜厚を表4に記載の通りに変えてφ/dを変えた以外は実施例4と同様にした。
[Influence on friction coefficient of φ / d]
In Examples 4, 21, and 22 and Comparative Examples 10 to 14, the influence of φ / d on the friction coefficient was evaluated. Examples 21 and 22 and Comparative Examples 10 to 14 were the same as Example 4 except that the film thickness of the coating composition was changed as shown in Table 4 to change φ / d.
実施例4、21、22及び比較例10〜14で得られた摩擦係数の評価を表4に示し、φ/dと摩擦係数との関係を図10に示す。表3中、◎は摩擦係数0.03未満であり、○は摩擦係数0.03以上0.05未満であり、△は摩擦係数0.05以上0.08未満であり、×は摩擦係数0.08以上である。表4及び図10より、φ/dが0.5〜3である実施例4、21、22では、比較例10〜14に対して摩擦係数が著しく低減し、優れた摩擦低減効果が示された。また、実施例4、21、22は、被膜の油吸収量について、比較例10〜14に対して優れていた。 The evaluation of the friction coefficient obtained in Examples 4, 21, 22 and Comparative Examples 10 to 14 is shown in Table 4, and the relationship between φ / d and the friction coefficient is shown in FIG. In Table 3, ◎ is a friction coefficient of less than 0.03, ◯ is a friction coefficient of 0.03 or more and less than 0.05, Δ is a friction coefficient of 0.05 or more and less than 0.08, and x is a friction coefficient of 0.08 or more. From Table 4 and FIG. 10, in Examples 4, 21, and 22 where φ / d is 0.5 to 3, the friction coefficient was remarkably reduced compared to Comparative Examples 10 to 14, and an excellent friction reducing effect was shown. In addition, Examples 4, 21, and 22 were superior to Comparative Examples 10 to 14 in the oil absorption amount of the coating.
[浮動ライナ式フリクション測定用エンジンを用いたフリクション評価]
本発明の被膜組成物の組成を最適化した実施例23の被膜組成物及び比較例1の被膜組成物について、浮動ライナ式フリクション測定用エンジンを用いてフリクション低減効果を確認した。
実施例23の被膜組成物の組成を表5に示す。
[Friction evaluation using floating liner type friction measurement engine]
Regarding the coating composition of Example 23 and the coating composition of Comparative Example 1 in which the composition of the coating composition of the present invention was optimized, the friction reduction effect was confirmed using a floating liner type friction measurement engine.
The composition of the coating composition of Example 23 is shown in Table 5.
試験は以下の方法で行った:
(1)組成物に含まれる成分の混合物を、鋳造アルミAC8Aよりなるピストンのスカート表面に、100番のメッシュサイズのスクリーンを用いてスクリーン印刷を行い、180℃で90分間焼成してN-メチル-2-ピロリドンを揮発させることにより、膜厚約10μmの被膜組成物を形成したピストンを作製した。
(2)作製したピストンにピストンリングなどを取り付け、浮動ライナ式フリクション測定用エンジンに組み込み、摩擦損失を摩擦平均有効圧力(FMEP)(ピストンの運動により生じた摩擦仕事をエンジン行程容積で除した値)により評価した。ピストンと摺動する相手材には、面粗さが十点平均粗さ(Rz)で2〜4μmの鋳鉄シリンダライナを用いた。同装置では、シリンダライナにて結合された荷重測定用センサーによりピストンが上下方向に摺動する際にシリンダライナに加わる摩擦力を測定している。
(3)浮動ライナ式フリクション測定用エンジンにてフリクションを測定する際の試験条件は、エンジン回転数800〜2400rpm、負荷300〜900kPa、潤滑油温度80℃であった。
The test was conducted as follows:
(1) The mixture of the components contained in the composition was screen-printed on the skirt surface of the piston made of cast aluminum AC8A using a screen of No. 100 mesh size, and baked at 180 ° C for 90 minutes for N-methyl A piston on which a coating composition having a film thickness of about 10 μm was formed by volatilizing -2-pyrrolidone was produced.
(2) A piston ring, etc. is attached to the manufactured piston and incorporated into a floating liner type friction measurement engine, and friction loss is calculated as friction mean effective pressure (FMEP) (value obtained by dividing friction work generated by piston motion by engine stroke volume. ). For the mating material sliding with the piston, a cast iron cylinder liner having a surface roughness of 10 to 4 average roughness (Rz) of 2 to 4 μm was used. In this apparatus, the frictional force applied to the cylinder liner when the piston slides in the vertical direction is measured by a load measuring sensor coupled by the cylinder liner.
(3) Test conditions for measuring friction with a floating liner type friction measuring engine were an engine speed of 800 to 2400 rpm, a load of 300 to 900 kPa, and a lubricating oil temperature of 80 ° C.
実施例23及び比較例1の被膜組成物を用いた場合のFMEPの差を図11に示す。この図において、縦軸の値が正の場合にはフリクション低減効果が無く、負の値を示す場合にはフリクション低減効果があることを意味する。図11より、実施例23の被膜組成物は比較例1の被膜組成物に対して優れたフリクション低減効果を示した。 FIG. 11 shows the difference in FMEP when the coating compositions of Example 23 and Comparative Example 1 are used. In this figure, when the value on the vertical axis is positive, there is no friction reduction effect, and when the value is negative, it means that there is a friction reduction effect. From FIG. 11, the coating composition of Example 23 showed an excellent friction reducing effect with respect to the coating composition of Comparative Example 1.
本発明の被膜組成物を用いることにより、摩擦特性及び耐摩耗性などのフリクションを改善することが可能となる。 By using the coating composition of the present invention, it is possible to improve friction such as friction characteristics and wear resistance.
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