EP0422822B1 - Schmierölzusammensetzungen - Google Patents

Schmierölzusammensetzungen Download PDF

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Publication number
EP0422822B1
EP0422822B1 EP90310807A EP90310807A EP0422822B1 EP 0422822 B1 EP0422822 B1 EP 0422822B1 EP 90310807 A EP90310807 A EP 90310807A EP 90310807 A EP90310807 A EP 90310807A EP 0422822 B1 EP0422822 B1 EP 0422822B1
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EP
European Patent Office
Prior art keywords
lubricating oil
composition according
oils
oil
oil composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90310807A
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English (en)
French (fr)
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EP0422822A1 (de
Inventor
Shinichi Shirahama
Yuji Ikemoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Oil Corp
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Publication of EP0422822A1 publication Critical patent/EP0422822A1/de
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M147/00Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • C10M147/04Monomer containing carbon, hydrogen, halogen and oxygen
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/004Foam inhibited lubricant compositions
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
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    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/04Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
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    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06Perfluoro polymers
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
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    • C10N2040/02Bearings
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    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
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    • C10N2040/10Running-in-oil ; Grinding
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/243Cold working
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    • C10N2040/244Metal working of specific metals
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    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum
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    • C10N2040/244Metal working of specific metals
    • C10N2040/246Iron or steel
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    • C10N2040/247Stainless steel
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    • C10N2040/251Alcohol-fuelled engines
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Definitions

  • This invention relates to lubricating oil compositions and more particularly to lubricating oil compositions which have low tendency to foaming, i.e. excellent defoamability (defoaming ability), and are utilizable as engine oils, gear oils, hydraulic oils, automatic transmission oils and bearing oils.
  • lubricating oils are circulated through portions of an engine to be lubricated (lubricating portions) during operation of such portions and, as a result, the amount of oil uses is reduced. Therefore, the oils which have passed through the lubricating portions are then returned to a sump. Since the oils have air entrapped therein at the lubricating portions, the oils so returned ordinarily foam or bubble. If the foam in the oils is difficult to break down, it will gradually increase during the use of the oils and the oils will finally overflow the sump. Accordingly, defoamability is required in lubricating oils.
  • Antifoaming agents such as silicone oils and polyacrylates, have heretofore been added to base oils for the sake of improving the resulting lubricating oils in defoamability.
  • silicone oils are known to be good antifoaming agents, they have comparatively high solubility in light-fraction oils and they will impart remarkably low defoamability when used in light-fraction oils. Further, the silicone oils will deteriorate when used for a long period of time, when used under severe operating conditions or when used with certain chemical materials, thereby causing the silicone oils to lose their defoamability.
  • perfluoro ethers are known for use as base oils for synthetic lubricating oils, in for example FR-A-2 099 935, where they are used because of their resistance to heat and oxidation at high temperatures and contain aryl group terminated perfluoroethers as stabilizers, they have never been used, as such, as minor components in lubricating oils since they are hardly soluble in other mineral oils and synthetic oils.
  • perfluoroalkanes and other organic compounds containing perfluoroalkyl(ene) groups, including ether compounds, but which compounds are not perfluoro compounds may be used as foaming inhibitors for mineral oil-based lubricating oils.
  • a lubricating oil composition exhibiting antifoaming properties comprising as the base oil a mineral oil-based lubricating oil and/or a synthetic oil-based lubricating oil, and as an essential component a perfluoro ether in an amount by weight of 1 to 1000 ppm based on the total weight of the composition.
  • the present inventors have made intensive studies in attempts to achieve the object mentioned above and, as the result of their studies, they found that a lubricating oil composition including a perfluoroalkyl ether has excellent defoamability.
  • mineral oil-based lubricating oils for use herein are those produced by subjection of fractions obtained by atmospheric distillation or reduced pressure distillation of mineral oils, to any suitable refining treatment such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrodewaxing, sulfuric acid treatment , clay treatment and hydrorefining or to any suitable combination of such refining treatments.
  • suitable refining treatment such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrodewaxing, sulfuric acid treatment , clay treatment and hydrorefining or to any suitable combination of such refining treatments.
  • examples of synthetic oil-based lubricating oils to which the perfluoroethers can be added include alpha-olefin oligomers such as normal paraffins, isoparaffins, polybutene, polyisobutylene and 1-decene oligomers; alkylbenzenes such as a monoalkylbenzenes, dialkylbenzenes and polyalkylbenzenes; alkylnaphthalenes such as monoalkylnaphthalenes, dialkylnaphthalenes and polyalkylnaphthalenes; diesters such as di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate and ditridecyl glutarate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythrito
  • oils may be used singly or jointly.
  • the base oils mentioned above should have a viscosity at 40°C of preferably 2 to 1000 x 10 ⁇ 6m2/S.
  • Perfluoro ethers having various chemical structures can be used as an essential component in the lubricating oil composition of the present invention.
  • the perfluoro ethers may be any compound represented by the general formula R1-0 ⁇ R3-0 ⁇ n R2 and may be used singly or in mixtures thereof.
  • R1 and R2 may be identical with, or different from, each other and each represent a straight-chain or branched-chain perfluoroalkyl group having 1 to 4 carbon atoms
  • R3 represents a straight-chain or branched-chain perfluoroalkylene group having 1 to 4 carbon atoms
  • n is an integer of 2 or more, preferably 10 to 300.
  • Each of R1 and R2 is thus selected from a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoroisobutyl group, a perfluro-sec.butyl group and a perfluoro-tert.butyl group.
  • R3 may be selected from a perfluoromethylene group, a perfluoroethylene group, a perfluorotrimethylene group, a perfluoropropylene group, a perfluorotetramethylene group, a perfluorobutylene group, a perfluoro-1,3-dimethylethylene group, a perfluoro 1-methyltrimethylene group, and a perfluoro 2-methyltrimethylene group.
  • the perfluoro ether used in the present invention may contain different perfluoroalkylene groups in the molecule.
  • the different perfluoroalkylene groups present may form a random copolymer or a block copolymer.
  • the viscosity of the perfluoro ether used in the present invention is not particularly limited, but it is preferably in the range of 1 to 1000 x 10 ⁇ 5m2/s at 20°C, more preferably 20 - 2-200 x 15 ⁇ 5m2/s at 20°C. Further, the average molecular weight of the perfluoro ether is not particularly limited, but it is usually in the range of 500 to 50,000, preferably 1,800 to 10,000.
  • the lubricating oil composition of the present invention include the perfluoro ether in an amount by weight of 1-1000 ppm, preferably 3-100 ppm, based on the total weight of the composition.
  • the perfluoro ether in such a lubricating oil composition is less than 1 ppm by weight, the perfluoro ether will undesirably not exert a satisfactory defoaming effect, while in a case where the content of the perfluoro ether exceeds 1000 ppm by weight in such a lubricating oil composition, the perfluoro ether may undesirably separate out from the composition.
  • the lubricating oil compositions of the present invention may further include, as required, known additives for the purpose of further improving their properties or performance.
  • additives include, for example, antioxidants, detergent-dispersants, viscosity index improvers, pour point depressants, lubricity improvers, wear resistance agents, extreme pressure agents, corrosion inhibitors, metal-deactivators, antifoaming agents apart from the perfluoro ethers mentioned above, emulsifiers, demulsifiers, bactericides and colorants.
  • the lubricating oil compositions of the present invention have a particular advantage in that the perfluoro ethers which are essential components of the compositions will be less deteriorated by interaction with other additives to be used therewith than the heretofore known antifoaming agents, thereby enabling a wider-range of other additives to be present.
  • the total amount of these various additives used is ordinarily up to 50 % by weight, preferably up to 30 % by weight, based on the total weight of the composition.
  • the lubricating oils of the present invention may be for use as engine oils such as for a four-cycle gasoline engine, a land diesel engine, a marine diesel engine and a gas engine; as turbine oil such as for an industrial turbine, a marine turbine, or a gas turbine; as gear oil such as for an automobile gear box, an industrial gear box or an automatic transmission unit; as hydraulic oil; as compressor oil; as vacuum pump oils; as refrigerator oils; as metal working oils such as for cutting, grinding, rolling, pressing, drawing, throttling-ironing and forging; as slide guiding surface oils or as bearing oils.
  • engine oils such as for a four-cycle gasoline engine, a land diesel engine, a marine diesel engine and a gas engine
  • turbine oil such as for an industrial turbine, a marine turbine, or a gas turbine
  • gear oil such as for an automobile gear box, an industrial gear box or an automatic transmission unit
  • hydraulic oil as compressor oil
  • vacuum pump oils as refrigerator oils
  • metal working oils such as for cutting, grinding, rolling, pressing, drawing, throttling-
  • the lubricating oil compositions of the present invention contain a certain small amount of the perfluoro ether which impart excellent behaviour to the oil composition as follows:
  • a perfluoro ether (trade name, Fomblin Y25: viscosity 2.5 x 10 ⁇ 4m2/s at 20°C: molecular weight: 3000: produced by Asahi Glass Co., Ltd) was added in an amount by weight of 30 ppm based on the total oil, to an industrial bearing oil used as the base oil (mineral oil-based base oil whose viscosity was 2.2 x 10 ⁇ 4m2/s at 40°C) to obtain a lubricating oil composition (Example 1), while a silicone oil (viscosity: 3 x 10 ⁇ 3m2/s at 25°C), was added, instead of the perfluoro ether, in an amount by weight of 30 ppm based on the total oil, to the same industrial bearing oil as in Example 1 to obtain a lubricating oil composition (Comparative Example 1).
  • the thus obtained lubricating oil compositions were subjected to the following oxidizing test and then to the following foaming test, respectively. The test conditions are indicated below,
  • the oil compositions were each subjected to oxidition at 150°C for 120 hours in accordance with JIS K 2514 3.1.
  • a perfluoro ether (trade name, Fomblin Y45: viscosity, 2.5 x 10 ⁇ 4m2/S at 20°C: molecular weight, 3000: produced by Asahi Glass Co.,Ltd.) was added in an amount by weight of 30 ppm based on the total oil, to an automobile transmission oil as the base oil (mineral oil-based base oil whose viscosity is 1.4 x 10 ⁇ 5m2/S at 100°C) to obtain a lubricating oil composition (Example 2), while a polyacrylate instead of the perfluoro ether was added in an amount by weight of 200 ppm based on the total oil, to the same automobile transmission oil as in Example 2 to obtain a lubricating oil composition (Comparative Example 2).
  • the thus obtained lubricating oil compositions were subjected to the following oxidizing test and then to the same foaming test as in Example 1, respectively.
  • the oxidizing test conditions are indicated hereunder, and the results of the foaming test are
  • the oil compositions were each subjected to oxidation at 150°C for 100 hours in accordance with JIS K 2514 3.1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (9)

  1. Schmierölzusammensetzung mit antischäumenden Eigenschaften, die als Basisöl ein Schmieröl auf Mineralölbasis und/oder ein synthetisches Schmieröl auf synthetischer Ölbasis und als wesentliche Komponente einen Perfluoräther in Gewichtsmengen von 1 bis 1000 ppm, bezogen auf das Gesamtgewicht der Zusammensetzung, enthält.
  2. Schmierölzusammensetzung nach Anspruch 1, in der die Perfluorätherkomponente mindestens eine verbindung der allgemeinen Formel R₁ - O (̵ R₃ - O )̵ n R₂
    Figure imgb0004
    ist, in der R₁ und R₂ gleich oder verschieden sein können und jeweils eine gradkettige Perfluoralkylgruppe mit 1 bis 4 Kohlenstoffatomen oder eine verzweigtkettige Perfluoralkylgruppe mit 1 bis 4 Kohlenstotfatomen, R₃ mindestens eine gradkettige Perfluoralkylengruppe mit 1 bis 4 kohlenmtotfatomen oder verzweigtkettige Perfluoralkylengruppe mit 1 bis 4 Kohlenstoffatomen und n eine ganze Zahl von 2 oder mehr, vorzugsweise 10 bis 300 sind.
  3. Schmierölzusammensetzung nach Anspruch 2, wobei der Perfluoräther verschiedene Perfluoralkylengruppen als Gruppe R₃ in jedem Molekül unter Bildung eines statistischen Copolymeren eines Blockcopolymeren enthält.
  4. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche, wobei der Perfluoräther eine Viskosität von 1 - 1000 x 10⁻⁵m²/S bei 20° C, vorzugsweise 2 - 200 x 10⁻⁵m²/S besitzt.
  5. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche, wobei der Perfluoräther ein mittleres Molekulargewicht von 500 bis 50.000, vorzugsweise 1.800 bis 10.000 aufweist.
  6. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche, wobei der Perfluoräther in Gewichtsmengen von 3 bis 100 ppm, bezogen auf des Gesamtgewicht der Zusammensetzung, enthalten ist.
  7. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche, die ein Schmieröl auf Mineralölbasis enthält, das unter Schmierölen ausgewählt wird, die dadurch hergestellt sind, daß Fraktionen, die durch Destillation unter atmosphärischen oder vermindertem Druck von Mineralölen erhalten wurden, einer raffinierenden Behandlung, nämlich der Lösungsdeasphaltierüng, Lösungsextraktion, Hydrocrakking, Lösungsentwachsen, Hydrowachsen, Schwefelsäurebehandlung, Tonbehandlung, Hydrorefining, oder einer Kombination dieser Verfahrensstufen unterzogen werden.
  8. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche 1 bis 6, die ein Schmieröl auf synthetischer Ölbasis enthält, das aus alpha-Olefinoligomeren, Alkylbenzolen, Alkylnaphtalinen, Diestern, Polyolestern, Polyglycolen, Polyphenylethern, Triscresylphosphat und/oder Silikonölen ausgewählt wurde.
  9. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Schmieröl auf Mineralölbasis und/ oder ein Schmieröl auf synthetischer Ölbasis eine Viskosität von 2 bis 1000 x 10⁻⁶m²/S bei 40° C aufweist.
EP90310807A 1989-10-13 1990-10-03 Schmierölzusammensetzungen Expired - Lifetime EP0422822B1 (de)

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JP265222/89 1989-10-13
JP1265222A JPH03126790A (ja) 1989-10-13 1989-10-13 潤滑油組成物

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DK1029030T3 (da) 1997-10-21 2003-05-05 Solutia Inc Skumningsresistente carbonhydridoliesammensætninger
GB0001981D0 (en) * 2000-01-31 2000-03-22 Ici Materials Refrigerant lubricant compositions
US7098173B2 (en) * 2002-11-19 2006-08-29 General Motors Corporation Thermally stable antifoam agent for use in automatic transmission fluids
JP2008266656A (ja) * 2008-07-04 2008-11-06 Tonengeneral Sekiyu Kk 潤滑油組成物
JP5638431B2 (ja) * 2011-03-18 2014-12-10 Jx日鉱日石エネルギー株式会社 金属加工用潤滑油組成物
JP5638430B2 (ja) * 2011-03-18 2014-12-10 Jx日鉱日石エネルギー株式会社 極微量油剤供給式加工用油剤組成物
WO2017012909A1 (en) * 2015-07-17 2017-01-26 Solvay Specialty Polymers Italy S.P.A. Anti-foaming agents

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IT1218217B (it) * 1988-04-13 1990-04-12 Ausimont Spa Additivi antirust per lubaificanti o grassi a base di perfluoropolieteri
IT1228655B (it) * 1989-02-09 1991-06-27 Ausimont Srl Perfluoropolieteri aventi proprieta' antirust utili quali componenti o additivi di olii e grassi lubrificanti.

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DE69002724D1 (de) 1993-09-16

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