NO312680B1 - Smöreoljeblanding - Google Patents

Smöreoljeblanding Download PDF

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Publication number
NO312680B1
NO312680B1 NO19954708A NO954708A NO312680B1 NO 312680 B1 NO312680 B1 NO 312680B1 NO 19954708 A NO19954708 A NO 19954708A NO 954708 A NO954708 A NO 954708A NO 312680 B1 NO312680 B1 NO 312680B1
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Prior art keywords
oil
carbon atoms
mixture
hydrocarbon group
calculated
Prior art date
Application number
NO19954708A
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English (en)
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NO954708D0 (no
NO954708L (no
Inventor
Katsuya Arai
Satoshi Asano
Sadao Wada
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Tonen Corp
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Publication of NO954708D0 publication Critical patent/NO954708D0/no
Publication of NO954708L publication Critical patent/NO954708L/no
Publication of NO312680B1 publication Critical patent/NO312680B1/no

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    • C10M129/48Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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Description

1. Oppfinnelsens bakgrunn
Foreliggende oppfinnelse vedrører, som angitt i krav l's ingress, en smøreoljeblanding og mer spesielt en smøreolje-blanding med forbedrede friksjonsnedsettende egenskaper og slitresistens og som er egnet som anvendelse som en smøre-olje for forbrenningsmotorer, automatgir, opphengings- og servostyrehjul og spesielt som en smøreolje for forbrenningsmotorer.
2. Beskrivelse av beslektet teknikk
Smøreoljer blir vanligvis anvendt for drift av forbrenningsmotorer , drivmekanismer slik som automatiske gir, opphengings- og servostyringer og gir. Mer spesielt vil motor-olje være effektiv ved smøring av hovedsakelig glidende deler, slik som stempelringer og sylinderfåringer, lagre for en veivaksel eller veivstang, og ventiler innbefattende kammer og ventilløftere, for å kjøle maskinen, samt rense og dispergere forbrenningsprodukter og forhindre rustdan-nelse og korrosjon.
Således er forskjellige funksjoner krevd av motoroljer, og
i den senere tid har også bedre funksjoner blitt krevd når den ønskede virkningsgrad og motoreffekt blir høyere og høyere og driftsbetingelsene enda mer alvorlige. Under disse forhold blir vanligvis additiver slik som et anti-slitasjemiddel, metallisk detergent, askefritt dispergeringsmiddel og anti-oksidant innarbeidet i motoroljen for å tilfredsstille slike krav.
Da energitapet i friksjonsdelene hvori smøreoljen deltar er høy i motoren, blir smøreoljen vanligvis anvendt i kombinasjon med additiver slik som friksjonsmodifiserende bestand-deler (FM) for å nedsette friksjonstapene og forbedre brennstoff-forbruket (se eksempelvis Japansk patentpublika-sjon nr. 23595/1991). Ytterligere fordi motoroljen for biler anvendes under forskjellige betingelser med hensyn til oljetemperatur, motorhastighet og belastning, er det nødvendig med utmerkede friksjonsegenskaper under et vidt område av betingelser for ytterligere forbedring av brennstoff -forbruket .
Fra US 4.832.867 er det kjent en smøreolje bestående av en basisolje inneholdende minst en organofosfor komponent og en organomolybden komponent, ytterligere kan oljeblandingen inneholde et additiv slik som et salisylat. Den beskrevne smøreolje er beregnet for bruk blant annet i forbrenningsmotorer.
Foreliggende oppfinnelse er et resultat av undersøkelser utført i den hensikt å tilveiebringe en smøreoljeblanding med forbedret friksjonsnedsettende egenskaper i forhold til de vanlige smøreoljer som inneholder molybden-ditiokarbamat og fosforsyre-estere og er egnet for anvendelse som smøre-olje for forbrenningsmotorer, automatiske overføringer, opphengings- og servostyrehjul, spesielt som smøremiddel-olje for forbrenningsmotorer.
Sammendrag av oppfinnelsen
Etter omfattende undersøkelse utført i den hensikt å ut-vikle en smøreoljeblanding med forbedret friksjonsnedsettende egenskaper er det funnet av ovenfor nevnte hensikt kan oppnås med en smøreoljeblanding som inneholder en spe-siell fosforsyre-ester og/eller fosfonsyre-ester, svovlet oksymolybden-ditiokarbamat og et kalsiumsalisylat i nærmere angitte andeler. Oppfinnelsen er basert på dette resultat, og er særpreget ved det som er angitt i krav l's karakte-ristiske del, ytterligere trekk fremgår av krav 2-5.
Spesielt tilveiebringer oppfinnelsen en smøreoljeblanding som omfatter en basisolje inneholdende (A) 0,01-0,8 vekt%, regnet på hele blandingen, av minst én forbindelse valgt fra gruppen bestående av (a) fosforsyre-estere med den generelle formel:
hvori R<1>, R<2> og R3 kan være like eller forskjellige, og hver representerer et hydrogenatom eller en hydrokarbongruppe med 3-23 karbonatomer, med det forbehold at minst én av R<1->R<3> er en hydrokarbongruppe med 3-23 karbonatomer, og
(b) fosfonsyre-estere har den generelle formel:
hvori R<4>, R5 og R6 kan være like eller forskjellige, og hver representerer et hydrogenatom eller en hydrokarbongruppe med 3-23 karbonatomer, med det forbehold at minst én av R<4->R6 er en hydrokarbongruppe med 3-23 karbonatomer;
(B) 50-2000 ppm, regnet som molybden, av svovlet oksymolybden-ditiokarbamat med minst én hydrokarbongruppe
med 8-18 karbonatomer, og
(C) 0,3-2,5 vekt%, regnet på hele blandingen, av et kalsiumsalisylat med et totalt basistall på 10-100.
Detaljert beskrivelse av oppfinnelsen
Basisoljen som er egnet som hovedbestanddelen i smøreolje-blandingen ifølge oppfinnelsen er ikke spesielt begrenset. Basisoljer er de som vanligvis anvendes i vanlige smøre-oljer, slik som mineraloljer og syntetiske oljer.
Mineraloljene innbefatter eksempelvis 60 nøytralolje, 100 nøytralolje, 150 nøytralolje, 300 nøytralolje og 500 nøy-tralolje erholdt ved oppløsningsmiddel-raffinering eller hydrorefining, samt basisoljer med lavt hellepunkt frem-stilt ved fjerning av voks ved disse basisoljer for å forbedre lavtemperatur fluiditeten. De kan enten anvendes alene eller i form av en blanding av to eller flere i passende forhold.
De syntetiske oljer innbefatter eksempelvis poly-a-olefin oligomerer, diestere, polyolestere og polyglykolestere. De kan anvendes alene eller i form av en blanding. De er også anvendbare i form av en blanding av den ovenfor nevnte mineralolje. Blandevektforholdet av syntetisk olje til mineralolje er eksempelvis 80:20 til 20:80.
En egnet basisolje for anvendelse i blanding av foreliggende oppfinnelse er en som har en viskositet i området 3-20 cST ved 100°C. Spesielt foretrukne er hydrokrakkede produkter og/eller voksisomeriserte produkter inneholdende 3,0 vekt% eller mindre av en aromatisk bestanddel og som har et svovelinnhold på 50 ppm eller under og et nitrogeninnhold
på 50 ppm eller under.
I blandingen ifølge oppfinnelsen er komponenten (A) minst én forbindelse valgt fra gruppen bestående av:
(a) fosforsyre-estere med den generelle formel:
hvori R<1>, R2, og R<3> hver er som definert ovenfor, og (b) fosfonsyre-estere med den generelle formel:
hvori R<4>, R5 og R<6> er som definert ovenfor.
Gruppene R<1>, R<2> og R<3> i den ovenfor viste formel [1] kan være like eller forskjellige, og hver representerer et hydrogenatom eller en hydrokarbongruppe med 3-23 karbonatomer, med det forbehold at minst en av R<1->R<3> er hydrokar-bongruppen med 3-23 karbonatomer. Hydrokarbongruppene med 3-23 karbonatomer innbefatter lineære og forgrenede og cykliske alkyl og alkenylgrupper med 3-23 karbonatomer, arylgruppe med 6-23 karbonatomer, alkylarylgrupper med 7-23 karbonatomer og arylalkylgrupper med 7-23 karbonatomer. Eksempler innbefatter propyl, butyl, pentyl, heksyl, cyklo-heksyl, oktyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl, eikosyl, fenyl, xylyl, benzyl og fenetylgrupper.
Gruppene R<4>, R5 og R6 i den ovenfor viste formel [2] for fosfonsyre-esterne kan være like eller forskjellige, og hver representerer et hydrogenatom eller en hydrokarbongruppe med 3-23 karbonatomer, med det forbehold at minst•én av R<4->R<6> er en hydrokarbongruppe med 3-23 karbonatomer. Eksempler innbefatter de nevnt under henvisning til R<1>, R<2 >og R<3> i den ovenfor generelle formel [1].
Blandingen ifølge oppfinnelsen kan inneholde fosforsyre-estere enten alene eller i kombinasjon med to eller flere av disse og/eller fosfonsyre-estere, alene eller i kombinasjon med to eller flere av disse som komponent (A). Ytterligere kan en kombinasjon av en eller flere fosforsyre-estere med en eller flere fosfonsyre-estere også anvendes.
Blandingen ifølge foreliggende oppfinnelse må inneholde fosforsyre-esteren og/eller fosfonsyre-esteren som komponent (A) i en mengde på 0,01-0,8 vekt%, fortrinnsvis 0.05-0,5 vekt%, regnet på hele blandingen. Når mengden av (A) er under 0,01 vekt%, vil ikke tilstrekkelig lave friksjonsegenskaper oppnås, og når innholdet overstiger 0,8 vekt% er det ingen signifikant ytterligere forbedring av friksjonsegenskapene.
Det svovlede oksymolybden-ditiokarbamat (MoDTC) som inneholder minst én hydrokarbongruppe med 8-18 karbonatomer, anvendes som komponent (B). MoDTC har en struktur representert ved den følgende generelle formel:
hvor gruppene R<7> og R<8> i den viste generelle formel [3] hver representerer en hydrokarbongruppe med 8-18 karbonatomer. Hydrokarbongrupper med 8-18 karbonatomer innbefatter lineære og forgrenede alkyl og alkenylgrupper med 8-18 karbonatomer og cykloalkyl, aryl, alyklaryl og arylalkylgrupper med 8-18 karbonatomer. Eksempler innbefatter 2-etyl-heksyl, n-oktyl, nonyl, decyl, lauryl, tridecyl, palmityl, stearyl, oleyl, eikosyl, butylfenyl og nonyl-fenylgrupper. R<7> og R<8> kan være like eller forskjellige fra hverandre, m og n er positive heltall slik at summen av m + n er 4 .
I blandingen ifølge oppfinnelsen kan MoDTC anvendt som komponent (B) anvendes enten alene eller i kombinasjon med to eller flere av disse. Mengden av MoDTC ligger i området 50-2000 ppm, fortrinnsvis 100-1000 ppm (regnet som molybden) basert på hele blandingen. Når mengden av molybden er under 50 ppm, kan det ikke oppnås tilstrekkelig friksjonsnedsettende egenskaper, og når den er over 2000 ppm, er det ingen ytterligere signifikant forbedring i friksjonsegenskapene. Kalsiumsalisylatet med et totalt basistall på 10-100 anvendes som komponent (C) i blandingen ifølge oppfinnelsen. Kalsiumsalisylatet er eksempelvis representert med den føl-gende generelle formel:
hvor gruppen R<9> i den generelle formel [4] representerer en lineær, forgrenet eller cyklisk alkylgruppe med 8-23 karbonatomer slik som en oktyl, nonyl, decyl, dodecyl, pentadecyl, oktadecyl eller eikosylgruppe.
Kalsiumsalisylatet anvendt som komponent (C) kan anvendes enten alene eller i kombinasjon med to eller flere derav. Mengden av kalsiumsalisylatet ligger i området 0,3-2,5 vekt%, regnet på hele blandingen. Når mengden av (C) er under 0,3 vekt%, oppnås ikke tilstrekkelige lave friksjonsegenskaper, og når mengden overstiger 2,5 vekt%, vil slita-sjeresistensen nedsettes og askeinnholdet økes ugunstig.
Smøreoljeblandingen ifølge oppfinnelsen kan inneholde egnede additiver som vanligvis innarbeides i smøreoljen, slik som et askefritt detergent-dispergeringsmiddel, visko-sitetsindeksforbedrer, hellepunktundertrykker, anti-oksidant, rustinhibitor, korrosjonsinhibitor, anti-skumningsmiddel og andre anti-slitasje midler og friksjonsmodifiserende midler, i den grad at hensikten med foreliggende oppfinnelse ikke forstyrres.
Det askefrie detergent-dispergeringsmiddel innbefatter eksempelvis suksinimider, suksinamider, benzylaminer og deres borderivater og estere. De anvendes i en mengde på vanligvis 0,5-7 vekt%, regnet på hele blandingen.
Viskositetsindeks-forbedrere innbefatter eksempelvis poly-metakrylater, polyisobutylener, etylen/propylenkopolymerer
og hydrogeneret styren/butadienkopolymerer. De kan anvendes i en mengde på vanligvis 0,5-35 vekt%, regnet på hele blandingen. Anti-oksidantene innbefatter eksempelvis amin-anti-oksidanter slik som alkylerte difenylaminer, fenyl-a-naftylaminer og alkylerte a-naftylaminer og fenoliske anti-oksidanter slik som 2,6-di-t-butyl-4-metylfenol, 4,4<1->metylenbis(2,6-di-t-butyl-4-metyl-fenol) og 4,4'-metylenbis(2,6-di-t-butylfenol). De anvendes vanligvis i en mengde på 0,05-2 vekt%, regnet på hele blandingen.
Rustinhibitorene innbefatter eksempelvis alkenylravsyrer og delestere derav. Korrosjonsinhibitorene innbefatter eksempelvis benzotriazol and benzimidazol. Anti-skumningsmidlene kan eksempelvis innbefatte dimetylpolysiloksaner og poly-akrylater. De kan passende innarbeides i blandingen.
I følgende eksempler vil ytterligere illustrere foreliggende oppfinnelse.
Eksempler 1- 8 og sammenligningseksempler 1- 5 Friksjonskoeffisienten for smøreoljeblandingen ble bestemt som følger:
(1) Koeffisient (u) :
Friksjonskoeffisienten ble bestemt ved LFW-1 prøven under betingelser av 270 o/min, 30 kp/120°C og 10 min.
Basisoljen 150N-1 (med en viskositet ved 100°C på 5,7 mm<2>/s, innehold av aromatisk komponent 4,1 vekt%, svovelinnhold 11,0 ppm og nitrogeninnhold på 89,0 ppm) eller 150N-2 (med viskositet ved 100°C på 5,5 mm<2>/s, aromatisk komponentinnhold 0,5 vekt%, svovelinnhold 0,5 ppm og nitrogeninnhold 0,1 ppm) ble anvendt.
Hver av smøreoljeblandingene gjengitt i tabell 1 ble frem-stilt fra basisoljen, og friksjonskoeffisienten (p) ble bestemt. Resultatene er gjengitt i tabell 1-1 og 1-2. Som vist i eksemplene 1-8 i tabell 1-1 og sammenlignings-eksemplene 1-5 i tabell 1-2 utviser en smøreolje inneholdende kombinasjonen av salisylat, MoDTC og fosforsyre-ester i henhold til oppfinnelsen en signifikant lavere friksjons-koeffisient i forhold til en oljeblanding inneholdende kun to komponenter.
Smøreoljeblandingen ifølge oppfinnelsen har bedre lav-friksjonsegenskaper enn de for vanlige smøreoljer omfattende MoDTC og en fosforsyre-ester og er egnet for anvendelse som smøremiddelolje eksempelvis for forbrenningsmotorer, automatgir, opphengings- og servostyringshjul, spesielt som smøreolje for forbrenningsmotorer.

Claims (5)

1. Smøremiddelblanding inneholdende en basisolje, organofosfor- og organomolybdenforbindelser, karakterisert ved at blandingen inneholder: (A) 0,01-0,8 vekt%, regnet på hele blandingen, av minst én forbindelse valgt fra gruppen bestående av: (a) fosforsyre-estere med den generelle formel hvori R<1>, R2 og R3 kan være like eller forskjellige, og hver representerer et hydrogenatom eller en hydrokarbongruppe med 3-23 karbonatomer, med det forbehold at minst én av R<1->R3 er en hydrokarbongruppe med 3-23 karbonatomer, og (b) fosfonsyre-estere med den generelle formel: hvori R<4>, R5 og R<6> kan være like eller forskjellige, og hver representerer et hydrogenatom eller en hydrokarbongruppe med 3-23 karbonatomer, med det forbehold at minst én av R<4->R<6> er en hydrokarbongruppe med 3-23 karbonatomer, (B) (B) 50-2000 ppm, regnet som molybden, basert på hele blandingen av svovlet oksy-molybden-ditiokarbamat med minst én hydrokarbongruppe med 8-18 karbonatomer, og (C) 0,3-2,5 vekt%, regnet på hele blandingen, av et kalsiumsalisylat med et totalt basistall på 10-100.
2. Oljeblanding ifølge krav 1, karakterisert ved at basisoljen er en hydrokrakket olje og/eller voksisomerisert olje inneholdende 3,0 vekt% eller mindre, regnet på basisolje av en aromatisk bestanddel og med et svovelinnhold på 50 ppm eller mindre og med et nitrogeninnhold på 50 ppm eller mindre.
3. Oljeblanding ifølge krav 1, karakterisert ved at komponent (A) utgjør 0,05-0,5 vekt%, regnet på hele blandingen.
4. Oljeblanding ifølge krav 1, karakterisert ved at det svovlede oksymolybden-ditiokarbamat har formelen: hvor R<7> og R<8> hver uavhengig er en hydrokarbongruppe med 8-18 karboner, og summen av m + n er 4.
5. Oljeblanding ifølge krav 1, karakterisert ved at kalsiumsalisylatet har formelen: hvori R<9> er en lineær, forgrenet eller cyklisk alkylgruppe med 8-23 karbonatomer.
NO19954708A 1993-05-27 1995-11-21 Smöreoljeblanding NO312680B1 (no)

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JP5148669A JPH06336593A (ja) 1993-05-27 1993-05-27 潤滑油組成物
PCT/US1994/006001 WO1994028094A1 (en) 1993-05-27 1994-05-27 Lubricating oil composition

Publications (3)

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NO954708D0 NO954708D0 (no) 1995-11-21
NO954708L NO954708L (no) 1995-11-21
NO312680B1 true NO312680B1 (no) 2002-06-17

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EP (1) EP0707623B1 (no)
JP (1) JPH06336593A (no)
AU (1) AU696014B2 (no)
CA (1) CA2163207C (no)
DE (1) DE69411922T2 (no)
NO (1) NO312680B1 (no)
WO (1) WO1994028094A1 (no)

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JPH07197064A (ja) * 1993-12-30 1995-08-01 Cosmo Oil Co Ltd パワーステアリングフルード組成物
JP3454593B2 (ja) * 1994-12-27 2003-10-06 旭電化工業株式会社 潤滑油組成物
EP0783032A4 (en) * 1995-07-20 1998-12-23 Idemitsu Kosan Co LUBRICATING OIL COMPOSITION
JP4354014B2 (ja) * 1995-10-05 2009-10-28 出光興産株式会社 無段変速機用潤滑油組成物
EP0811674B1 (en) * 1995-12-22 2002-05-22 Japan Energy Corporation Lubricating oil for internal combustion engines
US7625847B2 (en) 2002-08-05 2009-12-01 Nippon Oil Corporation Lubricating oil compositions
WO2004013264A1 (ja) * 2002-08-05 2004-02-12 Nippon Oil Corporation 潤滑油組成物
US7563752B2 (en) 2002-08-05 2009-07-21 Nippon Oil Corporation Lubricating oil compositions
JP4373650B2 (ja) * 2002-08-05 2009-11-25 新日本石油株式会社 潤滑油組成物
US20070117726A1 (en) * 2005-11-18 2007-05-24 Cartwright Stanley J Enhanced deposit control for lubricating oils used under sustained high load conditions
JP5097737B2 (ja) 2009-03-27 2012-12-12 株式会社日立ハイテクノロジーズ 自動分析装置及びサンプル分注ノズル
JP5105557B2 (ja) * 2010-04-26 2012-12-26 東燃ゼネラル石油株式会社 内燃機関用潤滑油組成物
JP2010189657A (ja) * 2010-04-26 2010-09-02 Tonengeneral Sekiyu Kk 内燃機関用潤滑油組成物
JP2013209569A (ja) 2012-03-30 2013-10-10 Jx Nippon Oil & Energy Corp 潤滑油組成物

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US4171558A (en) * 1976-09-20 1979-10-23 Idemitsu Kosan Co., Ltd. Cutting oil composition for processing cemented carbide skiving hob
JPS5975995A (ja) * 1982-10-25 1984-04-28 Showa Shell Sekiyu Kk 耐摩耗性、極圧性及び摩擦特性にすぐれた潤滑組成物
JPH0662983B2 (ja) * 1986-03-17 1994-08-17 株式会社豊田中央研究所 潤滑油組成物
US4849123A (en) * 1986-05-29 1989-07-18 The Lubrizol Corporation Drive train fluids comprising oil-soluble transition metal compounds
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JP2602102B2 (ja) * 1989-09-20 1997-04-23 日本石油株式会社 内燃機関用潤滑油組成物
US5281347A (en) * 1989-09-20 1994-01-25 Nippon Oil Co., Ltd. Lubricating composition for internal combustion engine
ATE123517T1 (de) * 1991-05-01 1995-06-15 Lubrizol Corp Thermisch stabile zusammensetzungen und diese enthaltende schmiermitteln und funktionelle flüssigkeiten.

Also Published As

Publication number Publication date
NO954708D0 (no) 1995-11-21
EP0707623A4 (en) 1996-09-18
JPH06336593A (ja) 1994-12-06
CA2163207C (en) 2002-11-26
AU696014B2 (en) 1998-08-27
EP0707623A1 (en) 1996-04-24
AU6959494A (en) 1994-12-20
DE69411922T2 (de) 1998-12-17
CA2163207A1 (en) 1994-12-08
WO1994028094A1 (en) 1994-12-08
DE69411922D1 (de) 1998-08-27
EP0707623B1 (en) 1998-07-22
NO954708L (no) 1995-11-21

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