EP0286996B2 - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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Publication number
EP0286996B2
EP0286996B2 EP88105669A EP88105669A EP0286996B2 EP 0286996 B2 EP0286996 B2 EP 0286996B2 EP 88105669 A EP88105669 A EP 88105669A EP 88105669 A EP88105669 A EP 88105669A EP 0286996 B2 EP0286996 B2 EP 0286996B2
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EP
European Patent Office
Prior art keywords
acid esters
oil
fatty acid
composition
acid
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
EP88105669A
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German (de)
English (en)
French (fr)
Other versions
EP0286996B1 (en
EP0286996A2 (en
EP0286996A3 (en
Inventor
Dasai Masashi
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.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C—CHEMISTRY; METALLURGY
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/08—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing butene
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
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    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
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    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
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    • C10M137/08—Ammonium or amine salts
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02—Natural products
    • C10M159/08—Fatty oils
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    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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    • C10N2040/50—Medical uses

Definitions

  • the present invention relates to a lubricating oil composition, in particular it relates to a lubricating oil composition having excellent frictional characteristics, decreased in changes with time of the frictional characteristics and an excellent oxidation stability, which therefore is useful as a lubricating oil for use in various parts such as an automatic transmission, a continuously variable transmission, a brake of a tractor and a power steering.
  • a lubricating oil to be used in parts including a wet clutch or a wet brake of an automatic transmission, a continuously variable transmission and a tractor is required to have such properties that frictional characteristics, oxidation stability, corrosion resistance and rust resistance are good.and transmission torque is large.
  • An especially important requirement is that the ratio of coefficient of static friction ( ⁇ 0 ) to coefficient of kinematic friction ( ⁇ 1200 ) as a measure of frictional characteristics is small and further that the change with time of the above ratio is small.
  • a lubricating oil having a high coefficient of static friction and good in transmission torque has heretofore been known.
  • This lubricating oil has disadvantages in that frictional characteristics are not sufficiently satisfactory and shift shock is undesirably big.
  • GB-A-1 199 936 discloses a lubricating oil composition
  • a lubricating oil composition comprising a naphthene + paraffin base oil having an aromatic content (C A ) of less than 0,5 % by weight and a kinematic viscosity of 19.24 x 10 -6 m 2 /s (19,24 cSt).
  • the composition further comprises sulfur-containing compounds, amine salts of phosphoric acid esters and carboxylic acid esters.
  • the exact naphthene content is not specified in this reference.
  • FR-A-1 544 802 disclosed a combination of a mineral oil with phosphate additives, the mineral oil having a naphthene content of at least 25 % and a kinematic viscosity at 90°C of from 1,06 x 10 -6 m 2 /s to 2,44 x 10 -6 m 2 /s (1,06 to 2,44 cSt), and the aromatic content of the lubricating oil composition disclosed therein being 9,0 %.
  • the object of the present invention is to overcome the above problems and to provide a lubricating oil composition which is decreased in shift shock, is great in transmission torque, and further has a sufficiently high corrosion-preventing ability. and thus is suitable for use in lubrication of an automatic transmission.
  • this object can be attained by compounding a specified proportion of a specific friction modifier to a base oil having specified properties.
  • the present invention relates to a lubricating oil composition which comprises:
  • the base oil component (A) of the lubricating oil composition of the present invention is a mineral oil, preferably a deep dewaxed oil obtained by subjecting a purified oil to deep dewaxing treatment.
  • the base oil as the component (A) of the present composition has a naphthene content (% C N ) of at least 30 %, preferably 32 to 70 %, an aromatic content (% C A ) of not more than 2 %, preferably not more than 1 %, and a kinematic viscosity at 100 ° C of from 1,5 x 10 -6 to 30 x 10 -6 m 2 /s ( 1,5 to 30 cSt), preferably 2 x 10 -6 to 20 x 10 -6 m 2 /s (2 to 20 cSt).
  • the naphthene content is less than 30 %, frictional characteristics are reduced. If the aromatic content is more than 2 %, oxidation stability is poor and the change with time is undesirably large. Moreover, if the kinematic viscosity at 100° C is less than 1,5 x 10 -6 m 2 /s (1,5 cSt), the evaporation loss is undesirably large while on the other hand if it is more than 30 x 10 -6 m 2 /s (30 cSt), the power loss due to viscosity resistance is undesirably too large.
  • the base oil of the component (A) prefferably has such characteristics as required for the usual lubricating oil, for example, (1) proper viscosity characteristics. (2) good stability against oxidation, (3) good detergency and dispersancy, (4) good rust resistance and corrosion resistance and (5) good low temperature fluidity.
  • the base oil has a viscosity of at ieast 80, a pour point of not more than -30 ° C, and a total acid value of 0,1 mg KOH/g.
  • various mineral oils and synthetic oils can be used as long as they have the above specified properties.
  • Representative examples of the mineral oil which can be used as the base oil of the component (A) include a purified oil which is obtained by purifying a distillate oil by the usual method, said distillate oil having been obtained by atmospheric distillation of a paraffin base crude oil or an intermediate base crude oil, or by vacuum distillation of a residual oil resulting from the atmospheric distillation, and a deep dewaxing oil which is obtained by subjecting the above purified oil to deep dewaxing treatment.
  • the process for purification of the distillate oil is not critical, and various methods can be employed.
  • the distillate oil is purified by applying such treatments as (a) hydrogenation, (b) dewaxing (solvent dewaxing or hydrogenation dewaxing), (c) solvent extraction, (d) alkali distillation or sulfuric acid treatment, and (e) clay filtration, alone or in combination with one another. It is also effective to apply the same treatment repeatedly at multi-stages.
  • a mineral oil obtained by deep dewaxing i.e., deep dewaxed oil is particularly preferred as the base oil of the component (A).
  • This deep dewaxing is carried out for example by solvent dewaxing under severe conditions, and catalytic hydrogenation dewaxing using a Zeolite catalyst.
  • mineral oil As well as the aforementioned mineral oil, usual synthetic oils such as alkylbenzene, polybutene and poly( ⁇ -olefin), a synthetic oil containing saturated hydrocarbons having fused rings and/or non-fused rings-such as 1-(1-decalyl)-1-cyclohexylethane or mixtures thereof can be used as the base oil of the component (A).
  • synthetic oils such as alkylbenzene, polybutene and poly( ⁇ -olefin)
  • a synthetic oil containing saturated hydrocarbons having fused rings and/or non-fused rings-such as 1-(1-decalyl)-1-cyclohexylethane or mixtures thereof can be used as the base oil of the component (A).
  • the friction modifier as the component (B) of the present composition is added to the base oil as the component (A) in a proportion of 0,01 to 5 % by weight, preferably 0,1 to 2 % by weight based on the total weight of the composition. If the proportion of the friction modifier is less than 0,01 % by weight, its addition is not effective. On the other hand, if it is more than 5 % by weight, oxidation stability is undesirably reduced.
  • the friction modifier which is used as the component (B) of the present composition, at least one compound selected from the group consisting of phosphoric acid esters, phosphorous acid esters, amine salts of phosphoric acid esters, amine salts of phosphorous acid esters.
  • sorbitan fatty acid esters pentaerythritol fatty acid esters, tetraesters being excluded, glycerine fatty acid esters, trimethylolpropane fatty acid esters, triesters being excluded, glycol fatty acid esters, neopentyl glycol fatty acid diesters being excluded, carboxylic acid esters, dicarboxylic acid esters being excluded, metal salts of carboxylic acids, fats and oils. higher alcohols, and sulfur-containing compounds is used. These compounds can be used alone or in combination with one another.
  • R 1 and R 2 may be the same or different and are each an alkyl group having 4 to 30 carbon atoms, an aryl group, or an alkyl-substituted aryl group.
  • phosphoric acid esters and phosphorous acid esters include butylacid phosphate, 2-ethylhexylacid phosphate, laurylacid phosphate, oleylacid phosphate, stearylacid phosphate, dibutylhydrogen phosphite, dilaurylhydrogen phosphite, dioleylhydrogen phosphite, distearylhydrogen phosphite, and diphenylhydrogen phosphite.
  • the amine salts of phosphoric acid esters and phosphorous acid esters include the oleylamine salts, coconut amine salts, beef tallow amine salts of the above phosphoric acid esters and phosphorous acid esters.
  • sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monooleate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate and mixtures thereof.
  • pentaerythritol fatty acid esters include the monoesters, diesters or triesters of pentaerythritol or dipentaerythritol and fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolic acid and behenic acid, and mixtures thereof.
  • glycerine fatty acid esters include oleic monoglyceride, stearic monoglyceride, oleic diglyceride and mixtures thereof.
  • trimethylolpropane fatty acid esters include the monoesters or diesters of trimethylpropane and fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolic acid and behenic acid, and mixtures thereof.
  • glycol fatty acid esters include the monoesters of propylene glycol, trimethylene glycol, 1,4-butanediol or neopentyl glycol and fatty acids such as capric acid, lauric acid, palmitic acid, myristic acid, stearic acid, oleic acid, linolic acid and behenic acid, and mixtures thereof.
  • carboxylic acids aliphatic carboxylic acids, divalent carboxylic acids (dibasic acids) and aromatic carboxylic acids can be used.
  • the aliphatic carboxylic acids have 8 to 30 carbon atoms and may be saturated or unsaturated.
  • aliphatic carboxylic acids include pelargonic acid, lauric acid, tridecanic acid, myristic acid, palmitic acid, stearic acid, eicosanic acid, behenic acid, triacon-tanoic acid, undecylenic acid, oleic acid, linolic acid, linoleic acid, erucic acid, and oils and fats fatty acids (e.g., coconut oil fatty acid, and palm kernel oil fatty acid).
  • divalent carboxylic acid examples include octadecylsuccinic acid, octadecenylsuccinic acid, polybutenesuccinic acid, adipic acid, azelaic acid, sebacic acid and dodecane diacid.
  • aromatic carboxylic acids include salicylic acid.
  • carboxylic acid amide various compounds can be used.
  • carboxylic acids as described above and amine compounds e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexaethylenepentamine, heptaethyleneoctamine, tetrapropylenepentamine, hexabutyleneheptamine, and alkanolamines such as monoethanolamine, and diethanolamine
  • amine compounds e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexaethylenepentamine, heptaethyleneoctamine, tetrapropylenepentamine, hexabutyleneheptamine, and alkanolamines such as monoethanolamine, and diethanolamine
  • Carboxylic acid esters include aliphatic carboxylic acid esters.
  • the alkyl (e.g., methyl, ethyl, propyl, butyl, octyl, lauryl, and oleyl) esters of aliphatic carboxylic acids are described above are usually used.
  • carboxylic acid metal salts zinc laurate, zinc oleate, zinc stearate, zinc salt of coconut fatty acid, aluminum stearate and magnesium salicylate can be used.
  • both animal oils and vegetable oils can be used.
  • animal oils include lard, beef tallow and fish oil.
  • vegetable oils include soy bean oil, rapeseed oil, rice bran oil, palm oil, palm kernel oil and coconut oil.
  • octyl alcohol lauryl alcohol, myristyl alcohol, oleyl alcohol and stearyl alcohol can be used.
  • sulfur-containing compounds sulfurized oil, the reaction product of phosphorous sulfide and pinene can be used.
  • the above compounds can be used as the component (B), friction modifier, of the composition of the present invention.
  • phosphoric acid esters, phosphorous acid esters or their amine salts, carboxylic acid amides, glycerine fatty acid esters, sorbitan fatty acid esters, carboxylic acid metal salts and mixtures comprising two or more thereof are preferred.
  • composition of the present invention is obtained by adding a friction modifier as the component (B) to a base oil as the component (A). If desired, a viscosity index improver, an antioxidant, a detergent dispersant and so forth can be added to the composition of the present invention.
  • the type of the viscosity idex improver is not critical.
  • polymethacrylate, polyisobutene, polyalkylstyrene and an ethylene-propylene copolymer can be used.
  • polymethacrylate having a molecular weight of not more than 100 000, preferably not more than 50 000, which is excellent in shear stability and is able to prevent changes in viscosity for a long time is particularly suitable.
  • the amount of the viscosity indes improver added can be determined appropriately; usually, it is 0,5 to 15 % by weight, preferably 2 to 10 % by weight based on the total weight of the composition.
  • antioxidant compounds commonly used, such as phenol-based compounds, amine-based compounds, and zinc dithiophosphate can be used. Representative examples are 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), phenyl- ⁇ -naphthylamine, dialkyldiphenylamine, zinc di-2-ethylhexyldithiophosphate, zinc diamyldithiocarbamate, and pinene pentasulfide.
  • the amount of the antioxidant added is 0.01 to 2% by weight, preferably 0.05 to 1% by weight based on the total weigh of the composition.
  • the detergent dispersant e.g. an ashless detergent, and a metal detergent can be used.
  • a boron-containing ashless detergent can be used.
  • alkenylsuccinic acid imide, sulfonates, and phenates are preferred. Examples are polybutenylsuccinic acid imide, calcium sulfonate, barium sulfonate, calcium phenate, barium phenate, and calcium salicylate.
  • the amount of the detergent dispersant added is 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on the total weight of the composition.
  • a corrosion preventing agent e.g., a rubber swelling agent, and a defoaming agent can be added to the composition of the present invention.
  • initial frictional characteristics are good, that is, the ratio of coefficient of static friction to coefficient of kinematic friction is small, and the shock due to speed change is small. Changes with time of the frictional characteristics are small. Furthermore, the lubricating oil composition of the present invention is excellent in oxidation stability and corrosion resistance. Thus the lubricating oil composition of the present invention is suitable for miniaturization of a transmission and so forth.
  • the lubricating oil composition of the present invention is quite useful as a lubricating oil for use in an automatic transmission or a continuously variable transmission, or as a lubricating oil for use in parts including a wet clutch or a wet brake of an agricultural tractor.
  • lubricating oil composition of the present invention having characteristics as described above is useful as a lubricating oil to be used in a shock absorber, a power steering, an oil suspension and further in various construction machines.
  • Base Oils A to E shown below were used as the base oil.
  • To 89.3% by weight of each of Base Oils A to E were added 4.0% by weight of polymethyl methacrylate (weight average molecular weight 42,000), 0.5% by weight of 2,6-di-tert-butyl-4-methylphenol, 5.0% by weight of polybutenylsuccinic acid imide, 0.1% by weight of an anti-corrosion agent, 1.0% by weight of a rubber swelling agent and 1% by weight of a defoaming agent to prepare Basic Oils A to E.
  • Base Oil A 40% by weight of Base Oil A, 30% by weight of an oil obtained by subjecting a distillate from an intermediate base oil to hydrogenation treatment, and 30% by weight of 1-(1-decalyl)-1-cyclohexylethane.
  • the forced degredation was performed at 150°C for 24 hours according to Oxidation Stability Test of Lubricating Oil for Intemal Combustion Engine, JIS K 2514.
  • the state of corrosion of a copper plate was measured after 3 hours at 100°C according to JIS K 2513.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
EP88105669A 1987-04-11 1988-04-09 Lubricating oil composition Expired - Lifetime EP0286996B2 (en)

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JP62087933A JP2599383B2 (ja) 1987-04-11 1987-04-11 潤滑油組成物
JP8793387 1987-04-11
JP87933/87 1987-04-11

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DE3873587T3 (de) 2000-04-27
DE3873587D1 (de) 1992-09-17
DE3873587T2 (de) 1993-05-19
KR880012740A (ko) 1988-11-28
EP0286996B1 (en) 1992-08-12
JP2599383B2 (ja) 1997-04-09
JPS63254196A (ja) 1988-10-20
KR930010575B1 (en) 1993-10-28
EP0286996A2 (en) 1988-10-19
EP0286996A3 (en) 1989-01-18

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