EP0578435B1 - Modifizierung der Reibung synthetischer Getriebeöle - Google Patents
Modifizierung der Reibung synthetischer Getriebeöle Download PDFInfo
- Publication number
- EP0578435B1 EP0578435B1 EP93305125A EP93305125A EP0578435B1 EP 0578435 B1 EP0578435 B1 EP 0578435B1 EP 93305125 A EP93305125 A EP 93305125A EP 93305125 A EP93305125 A EP 93305125A EP 0578435 B1 EP0578435 B1 EP 0578435B1
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- EP
- European Patent Office
- Prior art keywords
- oil
- lubricant
- metal
- ppm
- additive
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- C10M2227/061—Esters derived from boron
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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Definitions
- This invention relates to improving the frictional characteristics of gear oils in which the base oil is, or contains a significant quantity of, a synthetic oil such as a polyalpha-olefin oil (PAO) or a synthetic ester oil.
- a synthetic oil such as a polyalpha-olefin oil (PAO) or a synthetic ester oil.
- Modern commercial large vehicles equipped with manual transmissions of the synchronizer type are typically operated with conventional mineral oil-based transmission lubricants.
- Such lubricants contain additives for wear protection, corrosion protection, and other beneficial property improvements.
- the level and type of additive used depends on the performance requirements of the oil, including low temperature properties, or wear protection.
- Performance designations which are used include API-GL4 and API-GL5. More recently PG1, PG2 and API-GL7 are being defined. Additionally a degree of demulsification may be preferred.
- API-GL4 and lower performance specifications may be met using conventional crankcase mineral oil lubricants containing conventional levels of zinc dialkydithiophosphates, sulfonates, or ashless dispersants.
- P/S essentially ashless formulations, although up to at least API-GL5 has been met by P/S formulations containing significant levels of alkali metal borates and metal sulfonates (e.g., OLOA 9750 additive).
- P/S refers to gear oil additive packages in which a phosphorus and sulfur-containing antiwear and/or extreme pressure additive system is employed.
- the additives used pursuant to this invention are alkali or alkaline earth metal salts of oil-soluble sulfonic acids, such as petroleum sulfonic acids, preferably alkylaryl sulfonic acids and, more preferably, alkylbenzene sulfonic acids.
- the metals of such salts preferably are those which have low toxicity and which present little or no concern from the environmental standpoint, namely, lithium, sodium, potassium, magnesium, and calcium.
- barium and strontium sulfonates can be used, if desired.
- API-GL5 gear oil compositions used in actual practice that apparently contain a metal sulfonate component.
- SPIRAX MB 90 trademark of the Shell Oil Companies
- barium believed to be in the form of a barium sulfonate corrosion inhibitor.
- the other type is based on use of gear oil additive packages containing high levels of potassium borate dispersion serving as an antiwear/extreme pressure agent. These packages are believed to contain low levels of calcium, presumably in the form of a sulfonate. These packages are apparently used primarily (if not exclusively) in conventional mineral oil stocks in forming finished gear oils. And in any event, the levels of the potassium borate used in the finished oils (e.g., 1-2 wt%) are sufficiently high as to seriously impair the results obtainable by the practice of this invention and thus are outside of the permissible concentrations of this invention.
- a gear oil lubricant having a kinematic viscosity at 100°C in the range of 4 to 32 mm 2 .s -1 (cSt), and preferably in the range of 8 to 20 mm 2 .s -1 (cSt), and comprising:
- finished gear lubricants of this invention manifests itself in a substantial increase in the number of cycles during which the test can be performed without poor synchronization of the gear changes.
- a finished synthetic oil-based gear oil devoid of a metal sulfonate additive may encounter substantial failure within 10,000 or 15,000 cycles.
- finished synthetic oil-based lubricants of this invention which contain a metal sulfonate component can achieve at least 50,000 and usually at least 100,000 cycles of trouble free operation in this test procedure.
- the gear oil additive package used as component b) may in fact satisfy the requirements for other performance specifications such as API-GL5, and including specifications not yet in being (or even envisioned) such as PG1, PG2 and API-GL7 or specifications of other countries such as comparable JIS gear oil standards, or the like.
- the specifications of API-GL4 are to be considered minimum performance levels for the package.
- API-GL7 For example, if the requirements of the API-GL7 specification are more stringent for the most part than, say, API-GL4, the fact that an additive package satisfies the API-GL7 requirements inherently satisfies the minimum performance requirements for use in the practice of this invention, whether or not the package has actually been subjected to the API-GL4 performance tests.
- a gear oil additive package which comprises (1) an oil-soluble phosphorus and sulfur-containing antiwear and/or extreme pressure additive complement and (2) at least one alkali or alkaline earth metal salt of an oil-soluble sulfonic acid; said gear oil additive package being further characterized in that when blended with a base oil having a kinematic viscosity in the range of 4 to 32 cSt at 100°C and composed of at least 25% by volume of (i) hydrogenated poly-alpha-olefin oligomer oil or (ii) synthetic ester oil, or (iii) a combination of (i) and (ii) to form a lubricant containing from 0.01 to 2 wt % of said metal salt, said gear oil additive package provides a lubricant composition that:
- Still another aspect of this invention is the method of beneficially modifying the frictional characteristics of a low-friction synthetic lubricant composition containing a gear oil additive package such that the lubricant composition satisfies or exceeds the specifications for API-GL4 service, but does not exhibit satisfactory friction properties for use in manual transmissions, particularly those of the synchronizer type.
- the method comprises including in such lubricant composition an amount in the range of 0.01 to 2 wt % based on the total weight of the lubricant of at least one metal salt of an oil-soluble sulfonic acid such that the friction properties of said lubricant are improved for use in manual transmissions, particularly those of the syn-chronizer type.
- the metal of the sulfonate salt preferably is lithium, sodium, potassium, magnesium, or calcium, or a combination of two or more such metals.
- barium and/or strontium sulfonates can be used if desired.
- the metal sulfonate can be employed as a separate component (e.g., as a "top-treat" to the base oil with which the additive package has been or will be blended) or as a component of the additive package itself.
- a separate component e.g., as a "top-treat" to the base oil with which the additive package has been or will be blended
- a component of the additive package itself e.g., as a "top-treat" to the base oil with which the additive package has been or will be blended
- additive packages it is possible to blend the metal sulfonate and the respective components of the additive package into the base oil individually or in various compatible sub-combinations.
- the base oils are composed partially or entirely of a low-friction fluid such as PAO base oil and/or a synthetic ester lubricating oil.
- the PAO fluids are usually formed by oligomerization or co-oligomerization of 1-alkene hydrocarbon having 6 to 20 and preferably 8 to 16 carbon atoms in the molecule and hydrogenation of the resultant oligomer. Hydrogenated oligomers formed from 1-decene are particularly preferred. Methods for the production of such liquid oligomeric 1-alkene hydrocarbons are known and reported in the literature. See for example US-A- Nos. 3,763,244; 3,780,128; 4,172,855; 4,218,330; and 4,950,822. Additionally, suitable hydrogenated 1-alkene oligomers of this type are available as articles of commerce, for example, from Ethyl Corporation and its affiliates under the trade mark ETHYLFLO.
- Synthetic ester oils are also well known and widely available in the marketplace.
- Typical synthetic ester oils include such materials as the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol).
- dicarboxylic acids e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer
- alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol
- esters include dibutyl adipate, di(1-ethylpropyl) adipate, di(1,3-dimethylbutyl) adipate, di(2-ethylhexyl) adipate, didodecyl adipate, di(tridecyl) adipate, di(2-ethylhexyl) sebacate, dilauryl sebacate, di-n-hexylfumarate, dioctyl sebacate, di(1-methylpropyl) azelate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, mixed C 9 and C 11 dialkyl phthalate, dibutyl sebacate, di(1-ethylpropyl) sebacate, di(eicosyl) sebacate, the 2-ethylhexyl
- synthetic esters which may be used as synthetic oils include those made from C 3 -C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol. Trimethylol propane tripelargonate and pentaerythritol tetracaproate serve as examples.
- Suitable commercially available products include Emkarate 911P (ICI, plc.), and KETJENLUBE synthetic oil (Akzo Chemicals).
- the base oils may contain up to 75%, preferably no more than 50%, and more preferably no more than 25% by weight of a mineral oil or other suitable oleaginous liquid of lubricating viscosity, provided the overall base lubricant is suitable for use in forming a finished gear lubricant that satisfies or exceeds the specifications for API-GL4 service, and provided further that the resultant finished oil remains amenable to friction improvement pursuant to this invention. It will be understood that most gear oil packages contain diluent oils or solvents for certain active ingredients or components.
- the finished gear oil lubricant may contain up to 75% by weight of a mineral oil or the like, plus an additional amount of diluent oil or solvent emanating from the additives or additive package used in formulating the finished lubricant.
- the metal sulfonates used in the invention are preferably overbased metal sulfonates, but the so-called neutral metal sulfonates can be used, if desired.
- Petroleum sulfonates are usually prepared by the sulfonation of suitable petroleum fractions with subsequent removal of acid sludge and purification followed by neutralization with the appropriate basic metal compound (e.g., oxide or hydroxide). Petroleum oxidates such as described in EP-A- 275,395 (published July 27, 1988) can be used in forming overbased sulfonates.
- Alkylaryl sulfonates are usually prepared by sulfonation of alkylated benzene or benzene analogs (toluene, naphthalene, phenothiazine, diphenyl oxide, or diphenyl sulfide), followed by workup and neutralization.
- alkylbenzenes suitable for producing the sulfonates can be formed by alkylating benzene with an oligomer or polymer such as tetrapropylene in the presence of an Friedel-Crafts catalyst.
- oligomer or polymer such as tetrapropylene
- Friedel-Crafts catalyst a number of highly suitable metal sulfonates are available as articles of commerce.
- Quantities ranging from as little as 0.01 % wt % up to as much as 2 % by wt % or more of the metal sulfonate based on the total weight of the finished lubricant can be employed. Ordinarily the amount used will not be greatly in excess of that amount needed to yield the friction performance desired in the particular finished gear oil lubricant in question. Thus often the amount will not be above 1 wt %, and in some cases will not exceed 0.5 wt %.
- the amount will be proportioned such that when the package is blended into the base oil at the recommended or desired concentration, the resultant finished oil will contain from 0.01 wt % up to 2 wt % or more, preferably up to about 1 wt %, and in some cases up to about 0.5 wt % of the metal sulfonate. It is to be noted that these proportions of the metal sulfonate are based on the active ingredient, and thus the weight of any solvent or diluent associated with the metal sulfonate as used should be subtracted from the additive weight when calculating the concentration of metal sulfonate in the finished oil or in the friction-improved additive package. However the total weight of the finished oil or of the completed additive package will include the weight of such solvent or diluent.
- API-GL4 and API-GL5 service are published in ASTM Publication STP-512A entitled “Laboratory Performance Tests for Automotive Gear Lubricants” (March 1987).
- a number of gear oil additive packages that provide API-GL4 or API-GL5 performance are available in the marketplace. They generally contain at least a sulfur-phosphorus antiwear or extreme pressure additive system, one or more antioxidants, one or more corrosion inhibitors, and an antifoam additive, and may, and preferably do, contain a dispersant additive.
- a gear oil additive package which comprises:
- a finished lubricant composition containing at least the foregoing components a), b), c) and d) constitutes still another embodiment of this invention.
- Such finished lubricant satisfies or exceeds the specifications for API-GL4 service, and preferably satisfies or exceeds the specifications for API-GL5 service.
- Component a) of the foregoing additive package and finished lubricant composition most preferably is a Mannich base which includes or, alternatively, consists of boronated Mannich base ashless dispersant.
- Yet another embodiment of this invention involves using as component a) a Mannich base dispersant and proportioning components a) and b) above in the additive package or in the finished lubricant composition such that the mass ratio (wt/wt) of nitrogen in the Mannich base dispersant to sulphur in the sulphur-containing antiwear and/or extreme pressure agent is in the range of 0.0005:1 to 0.5:1, and preferably in the range of 0.003:1 to 0.2:1.
- a Mannich base dispersant is employed as component a) and components a) and c) above are proportioned in the additive package or in the finished lubricant such that the mass ratio (wt/wt) of nitrogen in the Mannich base dispersant to phosphorus in the metal-free phosphorus-containing antiwear and/or extreme pressure agent is in the range of 0.005:1 to 5:1, and preferably in the range of 0.01:1 to 2:1.
- any of the above additive concentrates and finished lubricant compositions further comprise at least one oil-soluble demulsifying agent.
- any of the above additive concentrates and finished lubricant compositions further comprise at least one oil-soluble amine salt of a sulphur-free hydrocarbyl phosphoric acid.
- the lubricant compositions of this invention have a halogen content, if any, of no more than 250 ppm, preferably no more than 100 ppm, and more preferably no more than 30 ppm on a weight basis.
- the ZF.Synchronizer test has been designed for the evaluation of oil performance in commercially available synchromesh units under endurance conditions with the bulk lubricant temperature controlled at a relatively high level. While it is important to simulate fairly closely the actual conditions met in service, the need to produce a test result in an acceptable period has to be taken into account. Briefly, two halves of a transmission synchromesh unit are repeatedly brought together under conditions of known force and speed differential until failure occurs. Failure may be defined in terms of synchromesh performance or overall wear.
- the test rig used in the procedure was designed with consideration of work done by Socin and Walters, SAE Paper Number 680008 entitled “Manual Transmission Synchronizers”; Fano, CEC TLPG4 Chairman's Final Report, 1985, entitled “Synchromesh Test Method With Proposed Synchro Test Rig”; and Brugen, Thies and Naurian of Zahnradfabrik Friedrichshafen A.G. in a paper entitled “Einhne Des Schmierstoffes auf die Kunststoffmaschine Vonffygetrieben”.
- the two synchromesh units are assembled in a gear box which forms the oil reservoir and facilitates splash lubrication of components. Drive may be transmitted along the main shaft or via the layshaft gears to give an increased ratio.
- the input speed is kept constant by means of a DC drive control system and a large flywheel simulating vehicle inertia.
- the output shaft accelerates and decelerates the small flywheel which simulates clutch inertia.
- a pivot linkage connected to a pneumatic cylinder provides the actuating force which is measured by means of a load ring strain gauge.
- a small heater is used to control oil temperature.
- Torque transmitted through the output shaft can be measured to give an indication of the coefficient of friction between the synchronizing cones.
- the synchromesh units used are standard commercially available steel units with a molybdenum-based plasma spray coating on the inner surface of the outer synchro-ring.
- the syn-chromesh units are renewed before each test.
- the coefficient of friction for satisfactory synchronizer performance in the test is at least 0.065.
- Another performance criterion which may be used when performing the test for qualification purposes is excessive vibration of the gear box casing in the axial plane, a condition symptomatic of poor gear changes.
- the control and monitoring of the rig is coordinated by a process controller. During a test, which consists of 10 5 cycles, the number of poor changes is recorded. The test is terminated prematurely if this number becomes unacceptable.
- Test components may be evaluated by inspecting the friction surface of the inner synchronizer cone using a Perthometer stylus device both before and after test. Polishing of the metal surface or the build up of a glaze of decomposed lubricant or additive yields an unacceptably smooth surface finish. This in turn causes low frictional values during the gear change and can lead to clash of the sleeve and gear clutch teeth. Wear measurements are also made on the test components.
- reaction vessel To a reaction vessel are charged 38.0 parts of sulphurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
- Primene® 81-R amine a tert-alkyl primary amine mixture in the C 12 -C 14 range; Rohm & Haas
- the mixture is stirred for 20 minutes without application of heat.
- another 4.9 parts of this tertiary alkyl monoamine product is added and the contents of the reaction vessel are maintained at 50°C for 1 hour with continuous stirring.
- 4.31 parts of oleic acid and 0.58 part of M530 defoamer an antifoam concentrate of Monsanto Company
- reaction vessel To a reaction vessel are charged 38.3 parts of sulphurized isobutylene, parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes. To this mixture are added 3.7 parts of Primene 81-R amine, 3.7 parts of C 16 and C 18 primary amines, 1.0 part of octyl amine, and 3.2 parts of process oil, and the mixture is stirred for 20 minutes while maintaining the contents of the reaction vessel at 50°C for 1 hour with continuous stirring.
- reaction vessel To a reaction vessel are charged 35.8 parts of sulphurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
- reaction vessel To a reaction vessel are charged 35.1 parts of sulphurized isobutylene, parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
- a gear lubricant is formulated using respective Examples A-D above as follows: Additive package 6.5% wt AMOCO 421 Magnesium Sulfonate 0.35% wt Diisodecyladipate 25% wt ETHYLFLO 174 PAO 58.15% wt ETHYLFLO 168 PAO 10.0% wt
- the above Shell HVI 115 mineral oil was a solvent neutral oil having a kinematic viscosity of 9 mm 2 .s -1 (cSt) at 100°C containing 1.0 HiTEC® 623 pour point depressant.
- the first seven tests in Table I i.e., Run Nos. 1-7) used SAE 80W viscosity grade formulations. Run Nos. 1-7 are comparative tests as none of these formulations contained a sulfonate additive. However, Run No. 8 used a formulation containing 0.5 wt% of HiTEC® 611 additive, an overbased calcium alkylbenzene sulfonate having a nominal TBN of 300 available commercially from Ethyl Petroleum Additives, Inc.
- the HiTEC 611 additive contains approximately 44% diluent oil.
- the formulation of Run No. 8 is an SAE 90 grade formulation useful as a total driveline fluid suitable for use in final drives such as hypoid differentials, as well as gear boxes. TABLE I Run No. % HiTEC 380 % PAO (I) % ESTER % MIN.
- OIL %PAO (II) ZF RESULTS 1 3.2 -- -- 96.8 -- PASS 2 3.2 96.8 -- -- -- FAIL 3 3.2 86.8 10 -- -- FAIL 4 6.5 86.8 10 -- -- FAIL 5 3.2 71.8 25 -- -- FAIL 6 3.2 71.8 25 -- -- FAIL 7 3.2 36.8 -- 60 -- FAIL 8 6.5 32.2 10 -- 50.8 PASS
- Run No. 8 shows that inclusion in the synthetic oil based fluid of a small amount of a metal sulfonate pursuant to this invention improved the frictional properties of the blend to such an extent that it passed the test.
- Table II summarizes the results of additional ZF.Synchronizer tests which demonstrate the practice and advantages of this invention.
- Run Nos. 11-14 represent the practice of this invention as these gear oils contained, respectively, 2.0, 1.0, 0.2 and 0.1% of a metal sulfonate (HiTEC® 611 additive).
- the gear oil contained, for comparative purposes, 1.0% of an alkenyl succinimide friction modifier of the type described in EP 20,037.
- the oil of Run No. 16 contained 3.5% of a polyisobutenyl succinimide ashless dispersant (HiTEC® 646 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd. and their affiliated companies). The foregoing percentages are on an "as received basis" and thus include solvent oils.
- oil-soluble is used in the sense that the component in question has sufficient solubility in the selected base oil in order to dissolve therein at ordinary temperatures to a concentration at least equivalent to the minimum concentration specified herein for use of such component.
- solubility of such component in the selected base oil will be in excess of such minimum concentration, although there is no requirement that the component be soluble in the base oil in all proportions.
- certain useful additives do not completely dissolve in base oils but rather are used in the form of stable suspensions or dispersions. Additives of this type can be employed in the compositions of this invention, provided they do not significantly interfere with the performance or usefulness of the composition in which they are employed.
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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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Lubricants (AREA)
Claims (9)
- Getriebeölschmiermittel mit einer kinematischen Viskosität bei 100°C im Bereich von 4 bis 32 mm2.s-1 (cSt), welches umfaßt:a) ein Basisöl, das mindestens 25 Gew.-% (i) eines hydrierten poly-α-Olefinoligomeröls oder (ii) eines synthetischen Esteröls oder (iii) einer Kombination von (i) und (ii) enthält,b) eine derartige Menge einer Getriebeölzusatzzubereitung, daß das Getriebeölschmiermittel den Spezifikationen für GL4-Service genügt oder diese übersteigt, undc) 0,01 bis 2 Gew.-%, bezogen auf das Gesamtgewicht des Schmiermittels, eines Alkali- oder Erdalkalimetallsalzes einer öllöslichen Sulfonsäure, wobei die Menge des verwendeten Metallsalzes ausreichend ist, um die Reibungseigenschaften des Schmiermittels zur Verwendung in manuellen Schaltungen, insbesondere solchen vom synchronisierenden Typ, zu verbessern,wobei das Schmiermittel, wenn überhaupt, nicht mehr als 100 ppm Metall in Form einer oder mehrerer metallenthaltender Additiv-Komponenten, die nicht das Metallsalz sind, und, bezogen auf das Gewicht, gegebenenfalls einen Borgehalt von nicht mehr als 1000 ppm aufweist.
- Schmiermittelzusammensetzung nach Anspruch 1, wobei die Komponente c) ein Calciumsalz einer öllöslichen Alkylbenzolsulfonsäure ist.
- Schmiermittelzusammensetzung nach Anspruch 1 oder 2, wobei die Komponente c) ein überbasisches Salz der Sulfonsäure ist.
- Schmiermittelzusammensetzung nach einem der Ansprüche 1 bis 3, wobei die Komponente a) mindestens 50 Gew.-% eines hydrierten poly-α-Olefinoligomeröls enthält.
- Getriebeölzusatzkonzentrat, das umfaßt:a) ein öllösliches, aschefreies Dispergiermittel, ausgewählt unter Succinimid, Bernsteinsäureesteramid und aschefreien Mannichbasen-Dispergiermitteln,b) ein öllösliches, metallfreies, Schwefel enthaltendes Mittel gegen Verschleiß und/oder für extremen Druck,c) ein öllösliches, metallfreies, Phosphor-enthaltendes Mittel gegen Verschleiß und/oder für extremen Druck, undd) mindestens ein Alkali- oder Erdalkalimetallsalz einer öllöslichen Sulfonsäure in einer derartigen Menge, daß eine durch Einmischen der Zusatzzubereitung in ein Basisöl gebildete Schmiermittelzusammensetzung eine kinematische Viskosität im Bereich von 4 bis 32 cSt bei 100°C aufweist und mindestens 25 Gew.-% (i) eines hydrierten poly-α-Olefinoligomeröls oder (ii) synthetischen Esteröls oder (iii) einer Kombination von (i) und (ii) enthält, um ein Schmiermittel zu bilden, das 0,01 bis 2 Gew.-% des Metallsalzes enthält, und eine Schmiermittelzusammensetzung liefert, welcheA) den Spezifikationen für API-GL4-Service genügt oder diese übersteigt,B) wenn überhaupt, nicht mehr als 100 ppm Metall neben dem Metall im Metallsalz enthält, undC) einen Borgehalt, wenn überhaupt, von nicht mehr als 1000 ppm aufweist.
- Konzentrat nach Anspruch 5 , wobei in d) das Metallsalz wie in Anspruch 2 oder 3 definiert ist.
- Konzentrat nach Anspruch 5 oder 6, wobei der Gesamthalogengehalt, wenn überhaupt, nicht mehr als 1000 ppm, bezogen auf das Gewicht, beträgt.
- Konzentrat nach Anspruch 7, wobei der Gesamthalogengehalt, wenn überhaupt, nicht mehr als 250 ppm, bezogen auf das Gewicht, beträgt.
- Verfahren zur Verbesserung der Reibungseigenschaften einer synthetischen Schmiermittelzusammensetzung mit geringer Reibung, welche zu mindestens 25 Gew.-% (i) hydriertes poly-α-Olefinoligomeröl oder (ii) synthetisches Esteröl oder (iii) eine Kombination von (i) und (ii) enthält, und eine Getriebeölzusatzzubereitung, damit das Getriebeölschmiermittel den Spezifikationen des API-GL4-Service genügt oder diese übersteigt, welche, wenn überhaupt, nicht mehr als 100 ppm Metall in Form eines oder mehrerer metallenthaltender Zusätze und einen Borgehalt aufweist, der, wenn überhaupt, nicht mehr als 1000 ppm beträgt, die jedoch keine ausreichende Reibungseigenschaften zur Verwendung in manuellen Schaltungen, insbesondere solchen von synchronisierenden Typ aufweist, wobei das Verfahren das Einbringen von 0,01 bis 2 Gew.-%, bezogen auf das Gesamtgewicht des Schmiermittels eines Alkali- oder Erdalkalimetallsalzes einer öllöslichen Sulfonsäure umfaßt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US91120392A | 1992-07-09 | 1992-07-09 | |
US911203 | 1992-07-09 |
Publications (2)
Publication Number | Publication Date |
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EP0578435A1 EP0578435A1 (de) | 1994-01-12 |
EP0578435B1 true EP0578435B1 (de) | 1997-10-15 |
Family
ID=25429898
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP93305125A Revoked EP0578435B1 (de) | 1992-07-09 | 1993-06-30 | Modifizierung der Reibung synthetischer Getriebeöle |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0578435B1 (de) |
JP (1) | JPH06179887A (de) |
CA (1) | CA2099314A1 (de) |
DE (1) | DE69314554T2 (de) |
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US8034754B2 (en) | 2005-03-31 | 2011-10-11 | The Lubrizol Corporation | Fluids for enhanced gear protection |
WO2012066575A1 (en) | 2010-11-19 | 2012-05-24 | Indian Oil Corporation Ltd. | A high performance gearbox lubricant with enhanced drain interval for heavy duty commercial vehicles and a process for producing the same |
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US5358650A (en) * | 1993-04-01 | 1994-10-25 | Ethyl Corporation | Gear oil compositions |
US5691283A (en) * | 1994-03-01 | 1997-11-25 | Ethyl Petroleum Additives Limited | Use of transmission and gear oil lubricants having enhanced friction properties |
TW291495B (de) | 1994-08-03 | 1996-11-21 | Lubrizol Corp | |
US5858929A (en) * | 1995-06-09 | 1999-01-12 | The Lubrizol Corporation | Composition for providing anti-shudder friction durability performance for automatic transmissions |
SG94669A1 (en) * | 1995-08-11 | 2003-03-18 | Lubrizol Corp | Combination of a sulfur compound and specific phosphorus compounds and their use in lubricating compositions, concentrates and greases |
GB9520295D0 (en) * | 1995-10-04 | 1995-12-06 | Ethyl Petroleum Additives Ltd | Friction modification of synthetic gear oils |
ZA97222B (en) * | 1996-01-16 | 1998-02-18 | Lubrizol Corp | Lubricating compositions. |
SG64414A1 (en) | 1996-01-16 | 1999-04-27 | Lubrizol Corp | Lubricating compositions |
KR100546531B1 (ko) * | 1997-10-01 | 2006-01-26 | 유니케마 케미에 비.브이. | 복합 에스테르, 이를 포함하는 배합물, 및 이들의 용도 |
AU9274198A (en) | 1997-10-03 | 1999-04-27 | Exxon Chemical Patents Inc. | Lubricating compositions |
JP4559601B2 (ja) * | 2000-09-01 | 2010-10-13 | ミネベア株式会社 | 防錆潤滑組成物を塗布したプラスチック成形物 |
JP2002285184A (ja) * | 2001-02-20 | 2002-10-03 | Ethyl Corp | ギア清浄用低燐配合 |
US6660695B2 (en) * | 2002-03-15 | 2003-12-09 | Infineum International Ltd. | Power transmission fluids of improved anti-shudder properties |
US6586374B1 (en) * | 2002-07-18 | 2003-07-01 | Primrose Oil Company | Engineered synthetic engine oil and method of use |
JP4808027B2 (ja) * | 2003-02-07 | 2011-11-02 | Jx日鉱日石エネルギー株式会社 | 変速機用潤滑油組成物 |
JP4328120B2 (ja) * | 2003-03-31 | 2009-09-09 | 住友重機械工業株式会社 | 揺動内接噛合型遊星歯車装置及びその耐久性向上方法 |
ATE479849T1 (de) * | 2003-05-30 | 2010-09-15 | Volkswagen Ag | Doppelkupplungsgetriebe |
US20070105728A1 (en) * | 2005-11-09 | 2007-05-10 | Phillips Ronald L | Lubricant composition |
US20070142248A1 (en) * | 2005-11-09 | 2007-06-21 | Degonla David J | Lubricant composition |
US8299003B2 (en) | 2005-11-09 | 2012-10-30 | Afton Chemical Corporation | Composition comprising a sulfur-containing, phosphorus-containing compound, and/or its salt, and uses thereof |
US20070142237A1 (en) * | 2005-11-09 | 2007-06-21 | Degonia David J | Lubricant composition |
US20070142660A1 (en) | 2005-11-09 | 2007-06-21 | Degonia David J | Salt of a sulfur-containing, phosphorus-containing compound, and methods thereof |
JP5363723B2 (ja) * | 2006-12-27 | 2013-12-11 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 潤滑油組成物 |
US20090093384A1 (en) * | 2007-10-03 | 2009-04-09 | The Lubrizol Corporation | Lubricants That Decrease Micropitting for Industrial Gears |
MX2013005269A (es) * | 2010-11-19 | 2013-06-03 | Chevron Usa Inc | Lubricante para equipo de percusion. |
RU2456335C1 (ru) * | 2011-06-09 | 2012-07-20 | Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (ОАО "ВНИИ НП") | Моторное масло |
KR101589399B1 (ko) | 2012-03-26 | 2016-01-27 | 더루우브리졸코오포레이션 | 싱크로메시 성능이 향상된 수동변속기 윤활제 |
CA2868780C (en) | 2012-03-26 | 2016-07-05 | The Lubrizol Corporation | Manual transmission lubricants with improved synchromesh performance |
CA2892812C (en) * | 2012-12-03 | 2021-01-26 | The Lubrizol Corporation | Industrial gear oils imparting reduced gearbox operating temperatures |
JP7247171B2 (ja) * | 2017-08-29 | 2023-03-28 | ビーエーエスエフ ソシエタス・ヨーロピア | 変速機の潤滑剤組成物 |
RU2708887C1 (ru) * | 2019-02-28 | 2019-12-12 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Состав и способ получения пакета присадок к гидравлическим маслам и всесезонное гидравлическое масло, его содержащее |
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- 1993-06-28 CA CA002099314A patent/CA2099314A1/en not_active Abandoned
- 1993-06-30 DE DE69314554T patent/DE69314554T2/de not_active Revoked
- 1993-06-30 EP EP93305125A patent/EP0578435B1/de not_active Revoked
- 1993-07-07 JP JP5191860A patent/JPH06179887A/ja active Pending
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US8034754B2 (en) | 2005-03-31 | 2011-10-11 | The Lubrizol Corporation | Fluids for enhanced gear protection |
WO2012066575A1 (en) | 2010-11-19 | 2012-05-24 | Indian Oil Corporation Ltd. | A high performance gearbox lubricant with enhanced drain interval for heavy duty commercial vehicles and a process for producing the same |
Also Published As
Publication number | Publication date |
---|---|
CA2099314A1 (en) | 1994-01-10 |
EP0578435A1 (de) | 1994-01-12 |
DE69314554T2 (de) | 1998-02-19 |
JPH06179887A (ja) | 1994-06-28 |
DE69314554D1 (de) | 1997-11-20 |
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