JP2007169597A - Lubricant composition, seizure-preventing agent, sensor and sensor-attaching structure - Google Patents
Lubricant composition, seizure-preventing agent, sensor and sensor-attaching structure Download PDFInfo
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- JP2007169597A JP2007169597A JP2006259641A JP2006259641A JP2007169597A JP 2007169597 A JP2007169597 A JP 2007169597A JP 2006259641 A JP2006259641 A JP 2006259641A JP 2006259641 A JP2006259641 A JP 2006259641A JP 2007169597 A JP2007169597 A JP 2007169597A
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- 239000000314 lubricant Substances 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 83
- 239000007787 solid Substances 0.000 claims abstract description 43
- 239000002199 base oil Substances 0.000 claims abstract description 29
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002562 thickening agent Substances 0.000 claims abstract description 16
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 12
- 229910052582 BN Inorganic materials 0.000 claims abstract description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001050 lubricating effect Effects 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 230000000573 anti-seizure effect Effects 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 229910000487 osmium oxide Inorganic materials 0.000 claims description 6
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 claims description 6
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 6
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- 229910003438 thallium oxide Inorganic materials 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 15
- 230000002265 prevention Effects 0.000 description 9
- 229960004643 cupric oxide Drugs 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- -1 and if necessary Chemical compound 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 230000003405 preventing effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 238000005259 measurement Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Lubricants (AREA)
Abstract
Description
本発明は、潤滑剤組成物に関するものであり、特に500℃以上の高温にさらされる可能性のある部品の焼付を防止するための潤滑剤組成物、この組成を有する焼付防止剤およびこの焼付防止剤を適用したセンサならびにセンサ取付構造に関する。 TECHNICAL FIELD The present invention relates to a lubricant composition, and in particular, a lubricant composition for preventing seizure of parts that may be exposed to a high temperature of 500 ° C. or higher, an anti-seizure agent having the composition, and an anti-seizure agent. The present invention relates to a sensor to which an agent is applied and a sensor mounting structure.
金属製部品のネジ部分等の必要箇所には、しばしば焼付防止を目的として、潤滑剤を塗布した後に組み立てられる。この金属製部品としては、被測定ガス中の特定ガス成分を検出するために内燃機関の排気管等に取り付けられるガスセンサの主体金具や、被測定ガス中の温度を検出するために排気管等に取り付けられる温度センサの主体金具等が挙げられる。また、このような潤滑剤としては、潤滑基油に固体潤滑剤を含んだペースト状潤滑剤や、潤滑基油を増ちょう剤で半固体化したグリースに固体潤滑剤を含んだペースト状潤滑剤が挙げられる(例えば、非特許文献1参照)。 Often, necessary parts such as screw parts of metal parts are assembled after applying a lubricant for the purpose of preventing seizure. The metal parts include a metal fitting for a gas sensor attached to an exhaust pipe of an internal combustion engine to detect a specific gas component in the gas to be measured, an exhaust pipe to detect the temperature in the gas to be measured, and the like. Examples include a metal shell of a temperature sensor to be attached. Also, as such a lubricant, a paste-like lubricant containing a solid lubricant in a lubricating base oil, or a paste-like lubricant containing a solid lubricant in a grease semi-solidified with a thickening base oil. (For example, refer nonpatent literature 1).
従来、500℃以上の高温にさらされる可能性のある金属製部品に適用されるペースト状潤滑剤には、銅、アルミニウム、ニッケルなどの金属を主成分とし、必要に応じて、二硫化モリブデンやグラファイトを組み合わせた固体潤滑剤を用いることが多い(例えば、特許文献1参照)。
これらの金属は、以下の作用により焼付きを防止すると考えられている。金属製部品の必要箇所にこれら金属を含むペースト状潤滑剤を塗布することで、均一な介在膜が金属製部品に形成される。そして、金属製部品が他部品に組付けられると、この介在膜が金属製部品と他部品との間に介在する。すると、金属製部品が高温にさらされた後、金属製部品を他部品から取り外す際(金属製部品と他部品とがしゅう動する際)には、これら金属自身の軟質さによる潤滑作用により金属製部品と他部品との焼付が防止されると考えられている。
Conventionally, paste-type lubricants applied to metal parts that may be exposed to high temperatures of 500 ° C. or higher are mainly composed of metals such as copper, aluminum, and nickel, and if necessary, molybdenum disulfide or A solid lubricant combined with graphite is often used (for example, see Patent Document 1).
These metals are believed to prevent seizure by the following actions. A uniform intervening film is formed on the metal part by applying a paste-like lubricant containing these metals to the necessary part of the metal part. When the metal part is assembled to another part, the intervening film is interposed between the metal part and the other part. Then, after the metal parts are exposed to high temperatures, when the metal parts are removed from other parts (when the metal parts and other parts are slid), the metal is lubricated by the softness of the metal itself. It is believed that seizure between manufactured parts and other parts is prevented.
しかし、金属製部品に形成された均一な介在膜が、金属製部品が他部品に組付けられる際に一部分に偏り、金属製部品と他部品との間の一部分のみに介在してしまう場合がある。すると、金属製部品と他部品とが直接接触する部位が存在してしまい、焼付が防止される効果が得られない場合がある。
このため、金属製部品が他部品としゅう動する際にも他部品との間に介在膜が全体に形成され、焼付防止効果を有するような、焼付防止用潤滑剤の開発が望まれている。
特に、高温で過酷な条件で使用されるセンサにふさわしい十分な焼付防止性能を有する焼付防止剤は、現在まで得られていない。
However, the uniform intervening film formed on the metal part may be biased to a part when the metal part is assembled to another part, and may be interposed only in a part between the metal part and the other part. is there. As a result, there is a portion where the metal part and the other part are in direct contact, and the effect of preventing seizure may not be obtained.
For this reason, even when a metal part slides with another part, the development of an anti-seizure lubricant is desired in which an intervening film is formed between the other part and has an anti-seize effect. .
In particular, no anti-seize agent having sufficient anti-seize performance suitable for a sensor used under severe conditions at high temperatures has not been obtained so far.
本発明が解決しようとする課題は、上記従来技術で挙げた問題点を解決できる潤滑剤組成物および、焼付防止剤ならびにセンサを提供することにある。すなわち、金属製部品と他部品とのしゅう動する際にも金属製部品と他部品との間に介在膜が全体に形成されやすく、かつ500℃以上の高温にさらされる可能性のある金属製部品に適用可能な潤滑剤組成物及びこれを用いる焼付防止剤およびこの焼付防止剤を適用するセンサならびにセンサ取付構造を提供することを課題とする。 The problem to be solved by the present invention is to provide a lubricant composition, an anti-seizure agent, and a sensor that can solve the above-mentioned problems in the prior art. In other words, when sliding between a metal part and another part, an intervening film is easily formed between the metal part and the other part, and the metal part may be exposed to a high temperature of 500 ° C. or more. It is an object of the present invention to provide a lubricant composition applicable to parts, an anti-seizure agent using the same, a sensor to which the anti-seize agent is applied, and a sensor mounting structure.
本発明は、以下の潤滑剤組成物を提供するものである。
本発明の潤滑剤組成物は、ビスマス、ビスマス化合物のうち、いずれか一つ以上からなる第1固体潤滑剤と、潤滑基油、もしくは潤滑基油および増ちょう剤(B成分)と、を含む潤滑剤組成物であって、前記第1固体潤滑剤の含有量をA、前記潤滑基油、もしくは前記潤滑基油及び前記増ちょう剤の含有量をBとしたとき、15質量%<A≦80質量%、20質量%≦B≦85質量%であることを特徴とする。
また、本発明の別の潤滑剤組成物は、ビスマス、ビスマス化合物のうち、いずれか一つ以上からなる第1固体潤滑剤と、有機樹脂と、を含む潤滑剤組成物であって、前記第1固体潤滑剤の含有量をA、前記有機樹脂の含有量をCとしたときに、15質量%<A≦80質量%、20質量%≦C≦85質量%であることを特徴とする。
前記した潤滑剤組成物は、さらにグラファイト、二硫化モリブデン、窒化ホウ素のうち、いずれか一つ以上からなる第2固体潤滑剤を含み、前記第2固体潤滑剤の含有量をDとしたときに、0.01質量%≦D≦60質量%となることができる。
前記した潤滑剤組成物は、第1固体潤滑剤がビスマス、またはビスマス化合物のいずれか1種であり、さらに、酸化銅、酸化タリウム、酸化イリジウム、酸化オスミウム、酸化ロジウム、酸化ルテニウムの少なくともいずれか1種からなる酸化防止剤を含有することができる。
前記した潤滑剤組成物は、焼付防止剤として用いることが有効である。
前記した焼付防止剤は、金属部品用として用いられることが好ましい。
特に被測定ガス中の状態を検出する検出素子と、該検出素子を保持する主体金具と、を有し、主体金具には、検出素子を被測定ガスに晒す際に排気管に取り付けるための取り付け部を有するセンサであって、少なくとも前記主体金具の前記取り付け部の外表面に前記した焼付防止剤が塗布されていることが好ましい。
さらに、被測定ガス中の状態を検出する検出素子と、該検出素子を保持する主体金具と、を有するセンサと、前記検出素子を被測定ガスに晒すために、該センサの該主体金具に形成される取り付け部を取り付ける排気管と、を有するセンサの取付構造において、前記センサと前記排気管との組付時には、前記主体金具の前記取付部の外表面と前記取付部に対応する前記排気管の外表面との間に前記した焼付防止剤が介在しており、前記取付部が該焼付防止剤の融点以上に加熱された後、前記取付部の外表面中央部に、ビスマス成分が残存することが好ましい。
The present invention provides the following lubricant composition.
The lubricant composition of the present invention comprises a first solid lubricant comprising at least one of bismuth and a bismuth compound, and a lubricant base oil, or a lubricant base oil and a thickener (component B). When the content of the first solid lubricant is A and the content of the lubricant base oil or the content of the lubricant base oil and the thickener is B, the lubricant composition is 15% by mass <A ≦ 80% by mass, 20% by mass ≦ B ≦ 85% by mass.
Another lubricant composition of the present invention is a lubricant composition comprising a first solid lubricant comprising at least one of bismuth and a bismuth compound, and an organic resin. When the content of 1 solid lubricant is A and the content of the organic resin is C, 15 mass% <A ≦ 80 mass% and 20 mass% ≦ C ≦ 85 mass%.
The above-described lubricant composition further includes a second solid lubricant composed of at least one of graphite, molybdenum disulfide, and boron nitride, and the content of the second solid lubricant is D. 0.01% by mass ≦ D ≦ 60% by mass.
In the above-described lubricant composition, the first solid lubricant is any one of bismuth and a bismuth compound, and at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide, and ruthenium oxide. One kind of antioxidant can be contained.
It is effective to use the above-described lubricant composition as an anti-seizure agent.
It is preferable that the above-described seizure inhibitor is used for metal parts.
In particular, it has a detection element for detecting the state in the gas to be measured and a metal shell for holding the detection element, and the metal shell is attached for attaching to the exhaust pipe when the detection element is exposed to the gas to be measured. It is preferable that the above-described anti-seizing agent is applied to at least the outer surface of the attachment portion of the metal shell.
Further, a sensor having a detection element for detecting a state in the gas to be measured and a metal shell for holding the detection element, and formed on the metal shell of the sensor to expose the detection element to the gas to be measured. In the sensor mounting structure, the exhaust pipe to which the mounting portion to be mounted is attached, and when the sensor and the exhaust pipe are assembled, the outer surface of the mounting portion of the metal shell and the exhaust pipe corresponding to the mounting portion The anti-seizure agent described above is interposed between the outer surface and the mounting portion is heated to a temperature equal to or higher than the melting point of the anti-seizing agent, and then the bismuth component remains in the central portion of the outer surface of the mounting portion. It is preferable.
本発明の潤滑剤組成物は、焼付防止効果、特に500℃以上の高温にさらされる可能性のある金属製部品、特にセンサの主体金具の取り付け部の焼付防止効果に優れている。 The lubricant composition of the present invention is excellent in an anti-seizure effect, in particular, an anti-seize effect of a metal part that may be exposed to a high temperature of 500 ° C. or more, particularly an attachment portion of a metal shell of a sensor.
本発明の潤滑剤組成物は、第1固体潤滑剤と、潤滑基油、あるいは潤滑基油および増ちょう剤を含む。
本発明の潤滑剤組成物に使用する第1固体潤滑剤は、ビスマス、ビスマス化合物のいずれか一つ以上を主成分とする。この成分を含む潤滑剤組成物を用いた焼付防止剤は、以下の作用により金属製部品の焼付を防止することができると発明者等は考えている。金属製部品の必要箇所にこの焼付防止剤を塗布することで、均一な介在膜が形成される。そして、上述の潤滑剤組成物を用いた焼付防止剤においても、金属製部品を他部品に組付ける際に一部分に偏ってしまい、金属製部品と他部品との間の一部分のみに介在するが、その後、金属製部品が高温にさらされた時に、焼付防止剤中のビスマスが溶融して金属製部品と他部品との間の全体にわたって浸透していき、介在膜を再度形成すると考えている。これにより、しゅう動する際には介在膜の潤滑作用により金属製部品と他部品との焼付きを防止することとなる。
The lubricant composition of the present invention comprises a first solid lubricant and a lubricating base oil, or a lubricating base oil and a thickener.
The first solid lubricant used in the lubricant composition of the present invention contains at least one of bismuth and a bismuth compound as a main component. The inventors consider that a seizure inhibitor using a lubricant composition containing this component can prevent seizure of metal parts by the following actions. A uniform intervening film is formed by applying the anti-seizing agent to the necessary part of the metal part. And even in the anti-seizure agent using the above-described lubricant composition, it is biased to a part when the metal part is assembled to another part, and is interposed only in a part between the metal part and the other part. Then, when the metal parts are exposed to high temperature, the bismuth in the anti-seizing agent melts and penetrates between the metal parts and the other parts, and the intervening film is formed again. . As a result, when sliding, the seizure between the metal part and other parts is prevented by the lubricating action of the intervening film.
なお、第1固体潤滑剤のうち、ビスマス化合物としては、酸化ビスマスが挙げられる。これらはいずれも市販されているもので、その平均粒径は100μm以下、好ましくは30μm以下である。本発明の潤滑剤組成物における上述の成分の含有量Aは、15質量%<A≦80質量%であり、好ましくは16質量%≦A≦40質量%である。Aが15質量%以下であると、焼付防止効果が得られない。一方、Aが80質量%を超えると、潤滑剤組成物としての流動性が失われ、部品摺動面への導入性が低下するため、結果として焼付防止効果が得られない。 In addition, bismuth oxide is mentioned as a bismuth compound among 1st solid lubricants. These are all commercially available, and their average particle size is 100 μm or less, preferably 30 μm or less. The content A of the above-described components in the lubricant composition of the present invention is 15% by mass <A ≦ 80% by mass, and preferably 16% by mass ≦ A ≦ 40% by mass. When A is 15% by mass or less, the seizure prevention effect cannot be obtained. On the other hand, if A exceeds 80% by mass, the fluidity as the lubricant composition is lost, and the ability to be introduced into the sliding surface of the component is lowered, and as a result, the seizure prevention effect cannot be obtained.
本発明の潤滑剤組成物に使用する潤滑基油としては、鉱物油、合成炭化水素油、ポリアルキレングリコール、ポリオールエステル、アルキル置換ジフェニルエーテル等およびそれらの混合油が挙げられるが、これらに限定されるものではない。 Examples of the lubricating base oil used in the lubricant composition of the present invention include, but are not limited to, mineral oils, synthetic hydrocarbon oils, polyalkylene glycols, polyol esters, alkyl-substituted diphenyl ethers, and mixed oils thereof. It is not a thing.
さらに、本発明の潤滑剤組成物に使用する増ちょう剤としては、グリースの増ちょう剤として利用可能な、カルシウムスルフォネート複合石けん、リチウム複合石けん、カルシウム複合石けん、リチウム石けん、カルシウム石けん、有機化ベントナイト、微粉末シリカ、脂肪族ジウレア、脂環族ジウレア、芳香族ジウレア、トリウレアおよびテトラウレア化合物が挙げられる。 Further, as a thickener used in the lubricant composition of the present invention, calcium sulfonate complex soap, lithium complex soap, calcium complex soap, lithium soap, calcium soap, organic, which can be used as a grease thickener. And bentonite, finely divided silica, aliphatic diurea, alicyclic diurea, aromatic diurea, triurea and tetraurea compounds.
この、潤滑基油、あるいは潤滑基油および増ちょう剤の含有量Bは20質量%≦B≦85質量%である。Bが20質量%未満であると、潤滑剤組成物としての流動性が失われ、部品しゅう動面への導入性が低下するため、結果として焼付防止効果が得られにくい。一方、Bが85質量%を超えると、固体潤滑剤の効果が発現しないため、焼付防止効果が得られにくい。 The content B of the lubricating base oil or the lubricating base oil and the thickener is 20% by mass ≦ B ≦ 85% by mass. When B is less than 20% by mass, the fluidity as the lubricant composition is lost, and the introduction property to the sliding surface of the component is lowered, and as a result, the seizure prevention effect is hardly obtained. On the other hand, when B exceeds 85% by mass, the effect of the solid lubricant is not exhibited, and thus the seizure prevention effect is hardly obtained.
そして、潤滑剤組成物に含まれる他の添加剤としては、抗酸化剤、極圧添加剤、清浄分散剤、防錆剤、腐食防止剤、消泡剤、希釈剤等が挙げられる。 Examples of other additives contained in the lubricant composition include antioxidants, extreme pressure additives, cleaning dispersants, rust inhibitors, corrosion inhibitors, antifoaming agents, and diluents.
また、本発明の別の潤滑剤組成物は、第1固体潤滑剤と、有機樹脂を含む。
この第1固体潤滑剤を含む別の潤滑剤組成物を用いた焼付防止剤は、上述の焼付防止剤と同様の作用により金属製部品の焼付を防止することができると考えている。
この別の潤滑剤組成物に使用する第1固体潤滑剤は、上述と同様のビスマス、ビスマス化合物のいずれか一つ以上を主成分とし、その含有量Aは、15質量%<A≦80質量%であり、好ましくは16質量%≦A≦40質量%である。
Another lubricant composition of the present invention includes a first solid lubricant and an organic resin.
The anti-seizure agent using another lubricant composition containing the first solid lubricant is considered to be able to prevent seizure of metal parts by the same action as the anti-seize agent described above.
The first solid lubricant used in this other lubricant composition is mainly composed of one or more of the same bismuth and bismuth compounds as described above, and the content A thereof is 15% by mass <A ≦ 80% by mass. %, Preferably 16% by mass ≦ A ≦ 40% by mass.
本発明の別の潤滑剤組成物に含まれる有機樹脂としては、ビスフェノールF型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、シリコーン樹脂およびチラノ樹脂が挙げられるが、これらに限定されるものではない。 Examples of the organic resin contained in another lubricant composition of the present invention include, but are not limited to, bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, silicone resin, and tyrano resin.
この、有機樹脂の含有量Cは20質量%≦C≦85質量%である。Cが20質量%未満であると、潤滑剤組成物としての流動性が失われ、部品しゅう動面への導入性が低下するため、結果として焼付防止効果が得られにくい。一方、Cが85質量%を超えると、固体潤滑剤の効果が発現しないため、焼付防止効果が得られにくい。 The organic resin content C is 20% by mass ≦ C ≦ 85% by mass. When C is less than 20% by mass, the fluidity as the lubricant composition is lost, and the introduction property to the sliding surface of the component is lowered, and as a result, the seizure prevention effect is hardly obtained. On the other hand, when C exceeds 85% by mass, the effect of the solid lubricant is not exhibited, so that the seizure preventing effect is hardly obtained.
そして、潤滑剤組成物に含まれる他の添加剤としては、紫外線吸収剤、抗酸化剤、湿潤分散剤、表面調整剤、防錆剤、腐食防止剤、消泡剤および硬化剤、希釈剤等が挙げられる。 Other additives contained in the lubricant composition include ultraviolet absorbers, antioxidants, wetting and dispersing agents, surface conditioners, rust inhibitors, corrosion inhibitors, antifoaming agents and curing agents, diluents, etc. Is mentioned.
本発明の潤滑剤組成物、および本発明の別の潤滑剤組成物には、上記第1固体潤滑剤と潤滑基油、あるいは潤滑基油および増ちょう剤、または有機樹脂に加えて、グラファイト、二硫化モリブデン、窒化ホウ素のうち、いずれか一つ以上からなる第2固体潤滑剤を含有させることができる。この第2固体潤滑剤をさらに含有させることで、ビスマスが金属製部品と他部品との間に浸透していく際に、同時に第2固体潤滑剤も浸透していき、第2固体潤滑剤が金属製部品と他部品との間に介在すると考えられている。これにより、潤滑性能をさらに向上させることができる。 In addition to the first solid lubricant and the lubricating base oil, or the lubricating base oil and thickener, or the organic resin, the lubricant composition of the present invention and the other lubricant composition of the present invention include graphite, A second solid lubricant composed of at least one of molybdenum disulfide and boron nitride can be contained. By further containing this second solid lubricant, when the bismuth penetrates between the metal part and the other parts, the second solid lubricant also penetrates at the same time. It is considered to be interposed between metal parts and other parts. Thereby, the lubrication performance can be further improved.
その1つであるグラファイトは市販されているもので、その平均粒径は100μm以下、好ましくは30μm以下である。上述の潤滑剤組成物における第2固体潤滑剤の含有量Dは、0.01質量%≦D≦60質量%であり、好ましくは10質量%≦D≦25質量%である。Dが60質量%以上であると、潤滑剤組成物としての流動性が失われ、部品しゅう動面への導入性が低下するため、結果として焼付防止効果が得られない。一方、0.01質量%未満であると、第2固体潤滑剤を含有させる効果が十分に得られないことがある。 One of them, graphite, is commercially available, and its average particle size is 100 μm or less, preferably 30 μm or less. The content D of the second solid lubricant in the above-described lubricant composition is 0.01% by mass ≦ D ≦ 60% by mass, and preferably 10% by mass ≦ D ≦ 25% by mass. When D is 60% by mass or more, the fluidity as the lubricant composition is lost and the introduction property to the sliding surface of the part is lowered, and as a result, the seizure prevention effect cannot be obtained. On the other hand, if it is less than 0.01% by mass, the effect of containing the second solid lubricant may not be sufficiently obtained.
ところで、本発明の潤滑剤組成物を用いたペースト状潤滑剤および本発明の別の潤滑剤組成物を用いたペースト状潤滑剤のうち、第1固体潤滑剤としてビスマスやビスマス化合物を用いたペースト状潤滑剤を金属製部品に塗布した後、金属製部品を更なる高温下(例えば700℃以上の温度下)にさらすと、金属製部品が酸化してしまい、強度が低下することがある。 By the way, a paste using bismuth or a bismuth compound as the first solid lubricant among the paste-like lubricant using the lubricant composition of the present invention and the paste-type lubricant using another lubricant composition of the present invention. If the metallic part is exposed to a further high temperature (for example, at a temperature of 700 ° C. or higher) after applying the lubricant to the metallic part, the metallic part may be oxidized and the strength may be reduced.
これは、以下の作用が生じていると発明者等は考えている。700℃以上の高温下にさらすと、ビスマスが酸化されて酸化ビスマスとなる(以下、酸化反応と言う)。しかしながら、金属製部品と他部品との間は閉空間となっているので、その閉空間の酸素分圧が低下することで、酸化反応を起こした酸化ビスマスが、再度ビスマスとなろうとする(以下、還元反応と言う)。すると、この還元反応を起こしたビスマスが、金属製部品表面に形成される不動態膜と反応してしまい、その結果、金属製部品を酸化させてしまうと考えている。 The inventors consider that this has the following effects. When exposed to a high temperature of 700 ° C. or higher, bismuth is oxidized to bismuth oxide (hereinafter referred to as oxidation reaction). However, since the space between the metal part and other parts is a closed space, the oxygen partial pressure in the closed space decreases, so that the bismuth oxide that has undergone the oxidation reaction tries to become bismuth again (hereinafter referred to as the bismuth). Is called a reduction reaction). Then, it is thought that the bismuth which caused this reduction reaction reacts with the passive film formed on the surface of the metal part, and as a result, the metal part is oxidized.
そこで、本発明の潤滑剤組成物の第1固体潤滑剤、および本発明の別の潤滑剤組成物の第1固体潤滑剤としてビスマス、ビスマス化合物を用いる際には、酸化銅、酸化タリウム、酸化イリジウム、酸化オスミウム、酸化ロジウム、酸化ルテニウムを含有させることが好ましい。上記酸化物により、酸素成分が閉空間に供給されることで閉空間の酸素分圧の低下を防止し、還元反応を抑制することができる。その結果、金属製部品が酸化されるのを抑制できる。この酸化物としては、製造上の安全性、コスト等を検討すると、酸化銅が好ましい。なお、これら酸化物の含有量Eは、4〜30質量%とすることが好ましい。 Therefore, when bismuth or a bismuth compound is used as the first solid lubricant of the lubricant composition of the present invention and the first solid lubricant of another lubricant composition of the present invention, copper oxide, thallium oxide, oxidation It is preferable to contain iridium, osmium oxide, rhodium oxide, and ruthenium oxide. With the oxide, the oxygen component is supplied to the closed space, so that the reduction of the oxygen partial pressure in the closed space can be prevented and the reduction reaction can be suppressed. As a result, it can suppress that metal parts are oxidized. As the oxide, copper oxide is preferable in view of manufacturing safety, cost, and the like. In addition, it is preferable that content E of these oxides shall be 4-30 mass%.
本発明の潤滑剤組成物は、焼付防止剤として特開平11−190720に示されるようなガスセンサを排気管に取り付けるためのナット部材のネジ部に用いられたり、以下に説明するようなガスセンサ1に用いられる。なお、本実施形態のガスセンサ1は、一実施形態であり、これに限られるものではない。このガスセンサ1は、自動車の排気管に装着されて排気ガス中の酸素の濃度を検出するガスセンサ1(酸素センサ)である。図1は、ガスセンサ1の全体構成を示す断面図である。 The lubricant composition of the present invention is used for a screw part of a nut member for attaching a gas sensor as shown in JP-A-11-190720 as an anti-seizure agent to an exhaust pipe, or for a gas sensor 1 as described below. Used. In addition, the gas sensor 1 of this embodiment is one Embodiment, It is not restricted to this. The gas sensor 1 is a gas sensor 1 (oxygen sensor) that is attached to an exhaust pipe of an automobile and detects the concentration of oxygen in the exhaust gas. FIG. 1 is a cross-sectional view showing the overall configuration of the gas sensor 1.
図1に示すように、ガスセンサ1は、先端部が閉じた有底筒状をなすセンサ素子2、センサ素子2に挿入されるセラミックヒータ3と、センサ素子2を内側にて保持する主体金具4を備える。なお、図1に示すセンサ素子2の軸に沿う方向のうち、測定対象ガス(排気ガス)に晒される先端部に向かう側(閉じている側、図中の下側)を「先端側」とし、これと反対方向(図中上側)に向かう側を「後端側」として説明する。 As shown in FIG. 1, the gas sensor 1 includes a sensor element 2 having a bottomed cylindrical shape with a closed end, a ceramic heater 3 inserted into the sensor element 2, and a metal shell 4 that holds the sensor element 2 on the inside. Is provided. In the direction along the axis of the sensor element 2 shown in FIG. 1, the side (closed side, lower side in the figure) facing the tip part exposed to the measurement target gas (exhaust gas) is referred to as “tip side”. The side toward the opposite direction (upper side in the figure) will be described as the “rear end side”.
このセンサ素子2は、酸素イオン伝導性を有する固体電解質体21と、その固体電解質体21の内面に、PtあるいはPt合金により形成された内部電極22と、固体電解質体21の外面に形成された外部電極23を有している。また、このセンサ素子2の軸線方向の略中間位置には、径方向外側に向かって突出するフランジ部24が設けられている。また、セラミックヒータ3は、棒状に形成されると共に、内部に発熱抵抗体を有する発熱部31を備えている。 This sensor element 2 is formed on a solid electrolyte body 21 having oxygen ion conductivity, an inner electrode 22 formed of Pt or a Pt alloy on the inner surface of the solid electrolyte body 21, and an outer surface of the solid electrolyte body 21. An external electrode 23 is provided. Further, a flange portion 24 that protrudes outward in the radial direction is provided at a substantially intermediate position in the axial direction of the sensor element 2. The ceramic heater 3 is formed in a rod shape and includes a heat generating portion 31 having a heat generating resistor therein.
主体金具4は、ガスセンサ1を排気管に取り付けるためのネジ部41(特許請求の範囲の取付部に相当)と、排気管への取り付け時に取付工具をあてがう六角部42を有している。また、六角部42の先端側には、ガスケット5が配置されている。そして、このネジ部41の表面には、本発明の焼付防止剤が塗布されており、排気管に取り付けられ、主体金具4が高温にさらされたとしても、排気管との焼付きを防止している。 The metal shell 4 has a screw part 41 (corresponding to an attachment part in claims) for attaching the gas sensor 1 to the exhaust pipe, and a hexagonal part 42 to which an attachment tool is applied when attaching to the exhaust pipe. Further, the gasket 5 is disposed on the tip side of the hexagonal portion 42. The surface of the screw portion 41 is coated with the anti-seizing agent of the present invention, and is attached to the exhaust pipe to prevent seizure with the exhaust pipe even when the metal shell 4 is exposed to high temperature. ing.
また、主体金具4には、先端側内周に径方向内側に向かって突出した金具側段部43が設けられており、この金具側段部43にパッキン6を介してアルミナ製の支持部材7が支持されている。なお、センサ素子2のフランジ部24が支持部材7上にパッキン8を介して支持される。また、支持部材7の後端側における主体金具4の内面とセンサ素子2の外面との間には、充填部材9が配設され、さらにこの充填部材9の後端側にスリーブ100および環状リング110が順次内挿されている。 Further, the metal shell 4 is provided with a metal-side stepped portion 43 projecting radially inward on the inner periphery of the front end side, and an alumina support member 7 is provided on the metal-side stepped portion 43 via a packing 6. Is supported. The flange portion 24 of the sensor element 2 is supported on the support member 7 via the packing 8. A filling member 9 is disposed between the inner surface of the metal shell 4 on the rear end side of the support member 7 and the outer surface of the sensor element 2, and a sleeve 100 and an annular ring are disposed on the rear end side of the filling member 9. 110 are sequentially inserted.
また、主体金具5の先端側には、複数のガス取入れ孔121を有する二重の金属製のプロテクタ120が取り付けられている。 A double metal protector 120 having a plurality of gas intake holes 121 is attached to the front end side of the metal shell 5.
また、主体金具4の後端側内側には内筒部材130の先端側が挿入されている。この内筒部材130は、先端側を環状リング110に当接させた状態で、主体金具4の後端部44を内側先端方向に加締めることで、主体金具4に固定されている。なお、主体金具4の後端部44を加締めることで、充填部材9がスリーブ100を介して圧縮充填される構造になっており、これによりセンサ素子2が筒状の主体金具4の内側に気密状に保持されている。 The front end side of the inner cylinder member 130 is inserted inside the rear end side of the metal shell 4. The inner cylinder member 130 is fixed to the metal shell 4 by caulking the rear end portion 44 of the metal shell 4 in the inner tip direction with the front end being in contact with the annular ring 110. In addition, by crimping the rear end portion 44 of the metal shell 4, the filling member 9 is compressed and filled via the sleeve 100, whereby the sensor element 2 is placed inside the cylindrical metal shell 4. It is kept airtight.
内筒部材130の後端側には、周方向に沿って所定の間隔で複数の大気導入孔131が形成されている。そして、内筒部材12の大気導入孔131を覆うように筒状のフィルタ140が配置されている。さらに、フィルタ140を覆うように外筒部材150が配置されており、外筒部材150のうち、フィルタ140に対応する位置には周方向に沿って所定の間隔で複数の大気導入孔151が形成されている。 On the rear end side of the inner cylinder member 130, a plurality of air introduction holes 131 are formed at predetermined intervals along the circumferential direction. And the cylindrical filter 140 is arrange | positioned so that the air introduction hole 131 of the inner cylinder member 12 may be covered. Furthermore, an outer cylinder member 150 is disposed so as to cover the filter 140, and a plurality of air introduction holes 151 are formed at predetermined intervals along the circumferential direction at positions corresponding to the filter 140 in the outer cylinder member 150. Has been.
また、内筒部材14の内側にはセパレータ160が配置されている。このセパレータ160は、素子用リード線170、180と、ヒータ用リード線190、200とを挿通するためのセパレータリード線挿通孔161が先端側から後端側にかけて貫通するように形成されている。 A separator 160 is disposed inside the inner cylinder member 14. The separator 160 is formed such that a separator lead wire insertion hole 161 for inserting the element lead wires 170 and 180 and the heater lead wires 190 and 200 penetrates from the front end side to the rear end side.
また、各リード線170、180、190、200は、詳細は図示しないが、導線を樹脂からなる絶縁皮膜にて被覆した構造を有しており、導線の後端側がコネクタに設けられるコネクタ端子に接続される。そして、素子用リード線170の導線の先端側は、センサ素子2の外面に対して外嵌される端子金具210の後端部と加締められ、素子用リード線180の導線の先端側は、センサ素子2の内面に対して圧入される端子金具220の後端部と加締められる。これにより、素子用リード線170は、センサ素子2の外部電極23と電気的に接続され、素子用リード線180は、内部電極22と電気的に接続される。他方、ヒータ用リード線190、200の導線の先端部は、セラミックヒータ3の発熱抵抗体と接合された一対のヒータ用端子金具230と各々接続される。 Although not shown in detail, each lead wire 170, 180, 190, 200 has a structure in which a conductive wire is covered with an insulating film made of resin, and the rear end side of the conductive wire is a connector terminal provided in the connector. Connected. The leading end side of the conducting wire of the element lead wire 170 is crimped with the rear end portion of the terminal fitting 210 that is externally fitted to the outer surface of the sensor element 2, and the leading end side of the conducting wire of the element lead wire 180 is The rear end portion of the terminal fitting 220 press-fitted into the inner surface of the sensor element 2 is crimped. Thereby, the element lead wire 170 is electrically connected to the external electrode 23 of the sensor element 2, and the element lead wire 180 is electrically connected to the internal electrode 22. On the other hand, the leading ends of the lead wires 190 and 200 for the heater are connected to a pair of heater terminal fittings 230 joined to the heating resistor of the ceramic heater 3, respectively.
そして、セパレータ160の後端側には、耐熱性に優れるフッ素ゴム等からなるシール材240が、外筒部材150を加締めることにより固定されている。このシール部材240には、軸線方向に貫くように4つのリード線挿通孔241が形成されている。 A sealing material 240 made of fluorine rubber or the like having excellent heat resistance is fixed to the rear end side of the separator 160 by caulking the outer cylinder member 150. The seal member 240 is formed with four lead wire insertion holes 241 so as to penetrate in the axial direction.
以下に実施例および比較例を挙げて本発明をさらに詳細に説明するが、これらは例示的なものであり、本発明はこれらによって何ら制限されるものではない。 The present invention will be described in more detail with reference to the following examples and comparative examples, but these are illustrative and the present invention is not limited by these.
表1に示す配合率で固体潤滑剤、潤滑基油、潤滑基油及び増ちょう剤、有機樹脂を配合して実施例1〜24および比較例25、26を作製した。実施例及び比較例の作製方法は特に限定されないが、一般的には、固体潤滑剤、潤滑基油、潤滑基油および増ちょう剤、有機樹脂を混合・攪拌し、必要に応じて3本ロールミルやホモジナイザーを用いて分散処理を行うことによって、作製できる。
固体潤滑剤、潤滑基油、潤滑基油および増ちょう剤、有機樹脂はいずれも、市販されているものであって、工業製品として入手可能なものである。
Examples 1 to 24 and Comparative Examples 25 and 26 were prepared by blending a solid lubricant, a lubricating base oil, a lubricating base oil and a thickener, and an organic resin at the blending ratio shown in Table 1. The production methods of Examples and Comparative Examples are not particularly limited, but in general, a solid lubricant, a lubricant base oil, a lubricant base oil and a thickener, and an organic resin are mixed and stirred, and a three-roll mill as required. Or by performing a dispersion treatment using a homogenizer.
Solid lubricants, lubricant base oils, lubricant base oils and thickeners, and organic resins are all commercially available and are available as industrial products.
*2 日本化学産業株式会社製
*3 鱗状黒鉛
*4 住鉱潤滑剤株式会社製
*5 電気化学工業株式会社製デンカボロンナイトライドHGP
*6 三共油化工業株式会社製SNH−46
*7 Krompton社製G−2000
*8 大日本インキ化学工業株式会社製EPICRON830S
*9 味の素ファインテクノ株式会社製アミキュアPN−23
*10 味の素ファインテクノ株式会社製アミキュアAH−154
*11 アルキレンモノグリシジルエーテルであって、25℃における粘度が6.5〜9.0mPa・sかつエポキシ当量が280〜320g/eqのもの
* 6 SNH-46 manufactured by Sankyo Oil Chemical Co., Ltd.
* 7 K-Rompton G-2000
* 8 EPICRON830S manufactured by Dainippon Ink & Chemicals, Inc.
* 9 Amicure PN-23 manufactured by Ajinomoto Fine Techno Co., Ltd.
* 10 Amicure AH-154 manufactured by Ajinomoto Fine Techno Co., Ltd.
* 11 Alkylene monoglycidyl ether having a viscosity at 25 ° C. of 6.5 to 9.0 mPa · s and an epoxy equivalent of 280 to 320 g / eq.
表1中の数値は、配合割合(質量%)を示す。表1中のグラファイトの平均粒径は、30μm以下である。 The numerical value in Table 1 shows a compounding ratio (mass%). The average particle size of graphite in Table 1 is 30 μm or less.
(焼付防止効果の評価)
本発明における潤滑剤組成物の焼付防止効果は、次のように評価した。
上記に述べたガスセンサ1に使用される主体金具4のネジ部41に約60mgの潤滑剤組成物を塗布し、試料用のナットに60N・mのトルクで締め付ける。なお、主体金具4は、SUS430製であり、試料用のナットは、SUS409L製である。さらに本評価は、ガスセンサ1に取り付ける前の主体金具4単体をナットに締め付けて行なった。その後、締結された主体金具4及びナットを500℃ないし700℃に保った電気炉で100時間加熱する。次いで室温まで冷却し、主体金具4をナットから緩める。これをそれぞれ10個ずつ行い、焼付が生じた主体金具4の個数の割合を百分率で表示し、焼付率(%)とした。なお、「焼付が生じた」とは、トルクレンチを使用して手で緩めた際に、ナットから主体金具4が外れない状況を指す。この場合に、さらに強い力で緩めると、主体金具4のネジ部41のねじ山がつぶれた状態となる。評価は、焼付率に基づいて、次のように行った。
◎:焼付率が0%
○:焼付率が0%を超え、5%以下
△:焼付率が5%を超え、20%以下
×:焼付率が20%を超える
実施例1〜36および比較例1〜4の評価結果を表2に示す。
(Evaluation of seizure prevention effect)
The seizure prevention effect of the lubricant composition in the present invention was evaluated as follows.
About 60 mg of the lubricant composition is applied to the screw portion 41 of the metal shell 4 used in the gas sensor 1 described above, and is tightened to a nut for a sample with a torque of 60 N · m. The metal shell 4 is made of SUS430, and the sample nut is made of SUS409L. Further, this evaluation was performed by tightening the metal shell 4 alone before being attached to the gas sensor 1 to a nut. Thereafter, the fastened metal shell 4 and the nut are heated for 100 hours in an electric furnace maintained at 500 ° C. to 700 ° C. Subsequently, it cools to room temperature and loosens the metal shell 4 from the nut. Ten pieces of each were performed, and the ratio of the number of metal shells 4 in which seizure occurred was displayed as a percentage, which was defined as a seizure rate (%). Note that “seizure has occurred” refers to a situation in which the metal shell 4 cannot be removed from the nut when it is loosened by hand using a torque wrench. In this case, when it is loosened with a stronger force, the thread of the threaded portion 41 of the metal shell 4 is crushed. The evaluation was performed as follows based on the baking rate.
A: Baking rate is 0%
○: The seizure rate exceeds 0% and 5% or less Δ: The seizure rate exceeds 5% and 20% or less ×: The seizure rate exceeds 20% The evaluation results of Examples 1-36 and Comparative Examples 1-4 It shows in Table 2.
第1固体潤滑剤としてビスマス、酸化ビスマスのいずれか一つを、第2固体潤滑剤としてグラファイトを、B成分として潤滑基油の鉱物油、または鉱物油を増ちょう剤のカルシウムスルフォネート複合石けんで増ちょうしたグリース、あるいはC成分としてビスフェノールF型エポキシ樹脂を、さらに酸化銅、酸化タリウム、酸化イリジウム、酸化オスミウム、酸化ロジウム、酸化ルテニウムのいずれか一種を用いた、本発明の実施例1〜24の潤滑剤組成物は、500℃、700℃共に良好な焼付防止性能を示した。これに対し、A成分が16質量%未満である比較例25、26はいずれも、500℃または700℃のいずれかが焼付防止性能に劣るものとなった。 One of bismuth and bismuth oxide as the first solid lubricant, graphite as the second solid lubricant, mineral oil of lubricating base oil as component B, or calcium sulfonate complex soap as a thickener Example 1 to Example 1 of the present invention using grease increased in step 1 or bisphenol F type epoxy resin as C component and further using any one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide, and ruthenium oxide. The lubricant composition of 24 showed good anti-seizure performance at both 500 ° C. and 700 ° C. On the other hand, in Comparative Examples 25 and 26 in which the A component was less than 16% by mass, either 500 ° C. or 700 ° C. was inferior in seizure prevention performance.
なお、このガスセンサ1のネジ部41を確認すると、外表面全面に、ビスマス成分が存在している。つまり、ガスセンサ1のネジ部41とナットとの組付時には、ネジ部41の外表面とナットの外表面との間に焼付防止剤が介在させる。そして、焼付防止剤の融点以上である700℃に加熱された後においても、ネジ部41の外表面全面に、ビスマス成分、がある。これにより、ネジ部41の外表面に形成した焼付防止剤の介在膜が、ナットに組付けた際にネジ部41とナットとの間の一部分のみに介在するが、その後、ガスセンサ1が高温にさらされた時に、焼付防止剤中のビスマスが溶融してネジ部41とナットとの間の全体にわたって浸透していき、介在膜を再度形成することになる。これにより、ネジ部41とナットが直接接触する箇所がなくなり、しゅう動する際にネジ部41とナットとの焼付を防止することとなる。なお、『ネジ部41の外表面中央部にビスマス成分が存在する』とは、ネジ部41山と谷との間の表面の中央部についてEDS分析を行い、ビスマスのピークが現れることでビスマス成分が存在するとしている。 In addition, when the screw part 41 of this gas sensor 1 is confirmed, the bismuth component exists in the whole outer surface. That is, when the screw part 41 and the nut of the gas sensor 1 are assembled, the anti-seizing agent is interposed between the outer surface of the screw part 41 and the outer surface of the nut. Even after heating to 700 ° C., which is equal to or higher than the melting point of the anti-seizing agent, there is a bismuth component on the entire outer surface of the screw portion 41. Thereby, the intervening film of the anti-seizing agent formed on the outer surface of the screw part 41 is interposed only in a part between the screw part 41 and the nut when assembled to the nut. When exposed, the bismuth in the anti-seizing agent melts and penetrates between the screw portion 41 and the nut, thereby forming an intervening film again. As a result, there is no place where the screw portion 41 and the nut are in direct contact, and seizure between the screw portion 41 and the nut is prevented when sliding. Note that “the bismuth component is present in the central portion of the outer surface of the screw portion 41” means that an EDS analysis is performed on the central portion of the surface between the crest and trough of the screw portion 41, and the bismuth component appears by the appearance of a bismuth peak. Is supposed to exist.
(耐食性の評価)
次に、本発明における潤滑剤組成物の耐食性評価を次のように行った。
まず、表3に示す配合率で固体潤滑剤、潤滑基油、潤滑基油及び増ちょう剤、有機樹脂、酸化銅、酸化タリウム、酸化イリジウム、酸化オスミウム、酸化ロジウム、酸化ルテニウムを配合して実施例27〜32を作製した。実施例の作製方法は、上記実施例1〜36と同様に行う。
(Evaluation of corrosion resistance)
Next, the corrosion resistance of the lubricant composition in the present invention was evaluated as follows.
First, blending solid lubricant, lubricating base oil, lubricating base oil and thickener, organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide, ruthenium oxide at the blending ratio shown in Table 3 Examples 27-32 were made. The manufacturing method of the example is performed in the same manner as in Examples 1 to 36.
*13 市販試薬(アメリカ製)
*14 市販試薬(日本製)
* 14 Commercially available reagents (made in Japan)
表3中の数値は、配合割合(質量%)を示す。
そして、上記に述べたガスセンサ1に使用される主体金具4のネジ部41に約60mgの潤滑剤組成物を塗布し、試料用のナットに60N・mのトルクで締め付ける。なお、主体金具4は、SUS430製であり、試料用のナットは、SUS409L製である。さらに本評価は、ガスセンサ1に取り付ける前の主体金具4単体をナットに締め付けて行なった。その後、締結された主体金具4及びナットを700℃に保った電気炉で100時間加熱する。次いで室温まで冷却し、主体金具4をナットから緩める。その後、主体金具4を半分割し、ネジ部41の断面をEDSにて成分のマッピングを行う。そして、成分マッピングの内、酸素が検出された厚みを酸化膜厚として算出する。評価は、酸化膜厚が20μm以上であるものを×、20μm未満であるものを○とした。また、表4の焼付率は上述した表2の評価に基づいて行った。
The numerical values in Table 3 indicate the blending ratio (mass%).
And about 60 mg of lubricant composition is apply | coated to the thread part 41 of the metal shell 4 used for the gas sensor 1 mentioned above, and it fastens to the nut for a sample with the torque of 60 N * m. The metal shell 4 is made of SUS430, and the sample nut is made of SUS409L. Further, this evaluation was performed by tightening the metal shell 4 alone before being attached to the gas sensor 1 to a nut. Thereafter, the fastened metal shell 4 and nut are heated in an electric furnace maintained at 700 ° C. for 100 hours. Subsequently, it cools to room temperature and loosens the metal shell 4 from the nut. Thereafter, the metal shell 4 is divided into two parts, and the cross section of the screw part 41 is subjected to component mapping by EDS. Then, the thickness in which oxygen is detected in the component mapping is calculated as the oxide film thickness. In the evaluation, those having an oxide film thickness of 20 μm or more were evaluated as “x”, and those having an oxide film thickness of less than 20 μm as “◯”. Moreover, the baking rate of Table 4 was performed based on evaluation of Table 2 mentioned above.
酸化銅、酸化タリウム、酸化イリジウム、酸化オスミウム、酸化ロジウム、酸化ルテニウムのいずれか一種を用いた実施例28〜32の潤滑剤組成物は、良好な耐食性を示した。これに対し、酸化銅等が含有されていない実施例27は、耐食性が劣るものとなった。 The lubricant compositions of Examples 28 to 32 using any one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide, and ruthenium oxide exhibited good corrosion resistance. On the other hand, Example 27 in which copper oxide or the like was not contained was inferior in corrosion resistance.
1・・・・・ガスセンサ
2・・・・・ガスセンサ素子
3・・・・・ヒータ
4・・・・・主体金具
7・・・・・支持部材
9・・・・・充填部材
100・・・スリーブ
120・・・プロテクタ
130・・・内筒部材
140・・・フィルタ
150・・・外筒部材
160・・・セパレータ
240・・・シール部材
136・・・フィルタ部
200、300・・・フィルタ被覆部材
201、301・・・被覆部
202、302・・・開口部
203、303・・・挿通部
DESCRIPTION OF SYMBOLS 1 ... Gas sensor 2 ... Gas sensor element 3 ... Heater 4 ... Metal shell 7 ... Support member 9 ... Filling member 100 ... Sleeve 120 ... Protector 130 ... Inner cylinder member 140 ... Filter 150 ... Outer cylinder member 160 ... Separator 240 ... Seal member 136 ... Filter part 200, 300 ... Filter coating Member 201, 301 ... Covering part 202, 302 ... Opening part 203, 303 ... Insertion part
Claims (8)
前記第1固体潤滑剤の含有量をA、前記潤滑基油、もしくは前記潤滑基油及び前記増ちょう剤の含有量をBとしたとき、15質量%<A≦80質量%、20質量%≦B≦85質量%であることを特徴とする潤滑剤組成物。 A lubricant composition comprising a first solid lubricant comprising at least one of bismuth and a bismuth compound, and a lubricating base oil, or a lubricating base oil and a thickener,
When the content of the first solid lubricant is A and the content of the lubricant base oil, or the content of the lubricant base oil and the thickener is B, 15% by mass <A ≦ 80% by mass, 20% by mass ≦ B ≦ 85 mass% Lubricant composition characterized by the above-mentioned.
該主体金具には、前記検出素子を被測定ガスに晒す際に排気管に取り付けるための取り付け部を有するセンサであって、請求項6記載の焼付防止剤が少なくとも前記主体金具の前記取り付け部の外表面に塗布されていることを特徴とするセンサ。 A detection element for detecting a state in the gas to be measured; and a metal shell for holding the detection element;
The metal shell is a sensor having an attachment portion for attaching the detection element to an exhaust pipe when the detection element is exposed to a gas to be measured, and the anti-seizure agent according to claim 6 is provided at least on the attachment portion of the metal shell. A sensor characterized by being applied to an outer surface.
前記センサと前記排気管との組付時には、前記主体金具の前記取り付け部の外表面と前記取付部に対応する前記排気管の外表面との間に請求項6記載の焼付防止剤が介在しており、
前記取付部が該焼付防止剤の融点以上に加熱された後、前記取付部の外表面中央部に、ビスマス成分が残存することを特徴とするセンサの取付構造。
A sensor having a detection element for detecting a state in the gas to be measured, a metal shell for holding the detection element, and an outer metal shell of the sensor for exposing the detection element to the gas to be measured. In the mounting structure of the sensor having an exhaust pipe for mounting the mounting portion,
The anti-seizing agent according to claim 6 is interposed between an outer surface of the mounting portion of the metal shell and an outer surface of the exhaust pipe corresponding to the mounting portion when the sensor and the exhaust pipe are assembled. And
A sensor mounting structure, wherein a bismuth component remains in a central portion of the outer surface of the mounting portion after the mounting portion is heated to a melting point or higher of the anti-seizing agent.
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JP2013076036A (en) * | 2011-09-30 | 2013-04-25 | Ngk Spark Plug Co Ltd | Lubricating coating composition, and fixing component for internal engine |
US9428708B2 (en) | 2011-09-30 | 2016-08-30 | Ngk Spark Plug Co., Ltd. | Lubricating coating composition and attachment component for internal combustion engine |
US9410468B2 (en) | 2013-04-30 | 2016-08-09 | Ngk Spark Plug Co., Ltd. | Temperature sensor attachment member treated with dry film lubricant |
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