EP1233054A1 - Automatic transmission fluids with improved anti-shudder properties - Google Patents

Automatic transmission fluids with improved anti-shudder properties Download PDF

Info

Publication number
EP1233054A1
EP1233054A1 EP02250876A EP02250876A EP1233054A1 EP 1233054 A1 EP1233054 A1 EP 1233054A1 EP 02250876 A EP02250876 A EP 02250876A EP 02250876 A EP02250876 A EP 02250876A EP 1233054 A1 EP1233054 A1 EP 1233054A1
Authority
EP
European Patent Office
Prior art keywords
automatic transmission
transmission fluid
fluid
friction
dispersant
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.)
Withdrawn
Application number
EP02250876A
Other languages
German (de)
French (fr)
Inventor
Sanjay Srinivasan
Rammath Iyer
Nubar Ozbalik
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.)
Ethyl Corp
Original Assignee
Ethyl Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ethyl Corp filed Critical Ethyl Corp
Publication of EP1233054A1 publication Critical patent/EP1233054A1/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • 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
    • C10M163/00Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M167/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/045Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • C10M2215/082Amides containing hydroxyl groups; Alkoxylated derivatives
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
    • C10M2215/224Imidazoles
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • 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
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049Phosphite
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/12Chemical after-treatment of the constituents of the lubricating composition by phosphorus or a compound containing phosphorus, e.g. PxSy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This invention relates to oil-based automatic transmission fluid compositions having excellent slip-stick characteristics, anti-shudder performance, and friction durability. More specifically, a preferred aspect of the invention relates to a use of the automatic transmission fluid in electronically controlled converter clutch (ECCC) applications.
  • ECCC electronically controlled converter clutch
  • US Patent 5,578,236, to Ethyl Corporation discloses a power transmission fluid with enhanced performance characteristics.
  • the power transmission fluid composition disclosed therein has, inter alia, an oil-soluble boron content of about 0.001 to about 0.1%, an oil soluble phosphorus content of about 0.005 to about 0.2%, and an oil soluble metal additive content of from 0 to about 100 ppm.
  • composition of the '236 patent comprises at least about 50 weight % hydrotreated mineral oils in the range of about 55N to about 125N, about 5 to 40 wt% of hydrogenated poly alpha olefin oligomer having a viscosity of about 2 to about 6 cSt at 100 ° C, about 5 to about 20 wt % of an acrylic viscosity index improver, a seal swell agent, an ashless dispersant, an oil soluble friction modifier, and an inhibitor selected from foam, copper corrosion (including thiadiazoles), rust, and oxidation inhibitors.
  • the finished composition has a Brookfield viscosity of 13,000 cP or less at - 40 ° C, an ASTM D-4683 viscosity of at least 2.6 mPa.s at 150 ° C, and a viscosity of at least 6.8 cSt at 100° C after 40 cycles in the FISST of ASTM D-5275.
  • the compositions disclosed are preferably devoid of sulfurized components.
  • US Patent 5,441,656 also to Ethyl Corporation, discloses an automatic transmission fluid for overcoming shudder problems in continuous slip torque converter clutches in automatic transmissions.
  • the automatic transmission fluid ("ATF") of the '656 patent includes, among other restrictions, a friction modifier content which contains an N-aliphatic hydrocarbyl substituted diethanolamine in which the N-aliphatic hydrocarbyl substituent having in the range of about 14 to about 40 carbon atoms, and an N-aliphatic hydrocarbyl substituted trimethylene diamine in which the N-aliphatic hydrocarbyl substituent is at least one straight chain aliphatic hydrocarbyl group having in the range of about 14 to about 20 carbon atoms.
  • Conventional copper corrosion inhibitors (including thiadiazoles) and other optional (e.g. lubricity, dye, pour point depressant, etc.) components may be present.
  • references fail to teach or suggest the combination of components of the present invention, including the combination of at least 0.10 wt % of a metal-containing detergent, a dispersant, and a friction modifier system including a mixture of at least two different friction modifiers.
  • a preferred mixture of friction modifiers is a mixture of an ethoxylated amine and an imidazoline.
  • Such a combination gives a friction durability of at least 200 hours as measured by the low speed ECCC friction durability test. It also gives a good balance of torque capacity, durability, initial shudder free performance (during a break in period) and continues to have a robust anti shudder durability over the lifetime of the fluid.
  • additives to automatic transmission fluid, including, among other things, extreme pressure agents, antiwear agents, antioxidant systems, corrosion inhibitor systems, metal deactivators, anti-rust agents, friction modifiers, dispersants, detergents, anti-foam agents, and viscosity index improvers.
  • extreme pressure agents including, among other things, extreme pressure agents, antiwear agents, antioxidant systems, corrosion inhibitor systems, metal deactivators, anti-rust agents, friction modifiers, dispersants, detergents, anti-foam agents, and viscosity index improvers.
  • additives include, among other things, extreme pressure agents, antiwear agents, antioxidant systems, corrosion inhibitor systems, metal deactivators, anti-rust agents, friction modifiers, dispersants, detergents, anti-foam agents, and viscosity index improvers.
  • the present invention relates to the improvement of friction durability, anti-shudder performance, and slip-stick performance by the inclusion into a final formulated automatic transmission fluid of a metal-containing detergent, a dispersant, and a friction modifier system including an ethoxylated amine and an imidazoline.
  • the fully formulated transmission fluid composition provides enhanced performance, especially for ECCC automatic transmissions
  • the transmission usually includes, inter alia, a clutch with plates, a torque converter, and a plurality of gears to alter the power delivered to the wheels by changing the gear ratio. It may also include a wet clutch.
  • This invention thus provides an automatic transmission fluid that exhibits excellent initial anti shudder performance, anti-shudder durability, and friction durability.
  • This invention also provides an automatic transmission fluid capable of passing the GM 3T40 Plate Friction and the DaimlerChrysler Friction Durability test.
  • the metal-containing detergent includes, by way of example, calcium-containing detergents such as calcium sulfonates,
  • the dispersant includes by way of example succinimide-type dispersants, which may be boronated or phosphorylated
  • the friction modifier system includes, also by way of example, an ethoxylated amine and an imidazoline.
  • the fluids of the present invention are used in formulating automatic transmission fluids which exhibit good frictional characteristics. In another embodiment, the fluids of the present invention are used in formulating automatic transmission fluids which exhibit excellent initial anti-shudder performance, and outstanding friction durability in the ECCC Friction durability test, as measured by the low speed SAE#2 friction rig.
  • the friction durability of an ATF is assessed through the use of an SAE #2 friction test machine.
  • This machine simulates the high-speed engagement of a clutch by using the clutch as a brake, thereby absorbing a specified amount of energy.
  • the energy of the system is chosen to be equivalent to the energy absorbed by the clutch in completing one shift in the actual vehicle application.
  • the machine uses a specified engagement speed, normally 3600 rpm, and a calculated inertia to provide the required amount of energy to the test clutch and fluid.
  • the clutch is lubricated by the fluid being evaluated, and each deceleration (i.e., braking) of the system is termed one cycle.
  • To evaluate friction durability many cycles are run consecutively. Increasing emphasis on friction durability by original equipment manufacturers (OEM's) has caused the total number of cycles required to demonstrate satisfactory friction durability to increase from several hundred in the 1980's to more than 30,000 in some proposed specifications.
  • Said methods comprise adding to, and operating in, an automatic transmission an automatic transmission fluid comprising (1) a major amount of a base oil and (2) a minor amount of an additive composition which comprises, as essential components at least Component (A); Component (B); and Component (C) as described below.
  • Component (A) Detergent
  • metal-containing detergents such as calcium sulfurized phenates, magnesium phenates, calcium sulfonates, and magnesium phenates are used in formulations according to the present invention.
  • Suitable metals include, but are not limited to, those found in Group 2A of the periodic table.
  • the amount of detergent is preferably elevated to a high degree, e.g. above 0.10 wt% and up to about 1.50 wt % for example, above 0.15 wt% to 1.50 wt% preferably between about 0.15 wt% and about 1.00 wt%, most preferably about 0.15-0.50 wt%.
  • These sulfurized phenates may be salts containing a stoichiometric amount of calcium, and also generally having a total base number (TBN) of not more than about 300 mg KOH/gram.
  • TBN total base number
  • One commercially available calcium phenate which is suitable for the practice of the instant invention is OLOA 216C, a calcium hydroxide salt of a sulfurized alkyl phenate having a nominal TBN of about 150, available from Oronite Division of Chevron Chemical Co. HiTEC® 614, a neutral calcium sulfonate available from Ethyl Corporation, Richmond, Virginia, is also suitable for use in the present invention.
  • the detergent is prepared as an overbased detergent. That is to say, in preparation, the detergent is reacted with a large amount of an inorganic base, e.g. calcium carbonate or magnesium carbonate, and is thus capable of absorbing a large excess of acidic products.
  • an inorganic base e.g. calcium carbonate or magnesium carbonate
  • One such suitable overbased calcium phenate which is suitable for the practice of the present invention is OLOA 219 C, with a total base number of about 260 also available from Oronite.
  • sulfonate detergents are used in the levels specified above.
  • One such suitable sulfonate is HiTEC® 611, an overbased calcium detergent with a TBN of about 300, also available from Ethyl Corporation.
  • a mixture of detergents such as a mixture of overbased calcium phenate and overbased calcium sulfonate, in roughly equal proportions.
  • Component (B) comprises at least one oil-soluble phosphorus or boron-containing ashless dispersant.
  • the phosphorus or boron-containing ashless dispersants can be formed by phosphorylating or boronating an ashless dispersant having basic nitrogen and/or at least one hydroxyl group in the molecule, such as a succinimide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, hydrocarbyl polyamine dispersant, or polymeric polyamine dispersant.
  • the polyamine succinimides in which the succinic group contains a hydrocarbyl substituent containing at least 30 carbon atoms are described for example in U.S. Pat. Nos. 3,172,892; 3,202,678; 3,216,936; 3,219,666; 3,254,025; 3,272,746; and 4,234,435.
  • the alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group.
  • the alkenyl succinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to, for example, about 180-220 degrees C.
  • the olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1-butene, isobutene and the like and mixtures thereof.
  • the more preferred source of alkenyl group is from polyisobutene having a gel permeation chromotography (GPC) number average molecular weight of up to 10,000 or higher, preferably in the range of about 500 to about 2,500, and most preferably in the range of about 800 to about 1,500.
  • GPC gel permeation chromotography
  • succinimide is meant to encompass the completed reaction product from reaction between one or more polyamine reactants and a hydrocarbon-substituted succinic acid or anhydride (or like succinic acylating agent), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
  • Alkenyl succinic acid esters and diesters of polyhydric alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups can be used in forming the phosphorus-containing ashless dispersants. Representative examples are described in U.S. Pat. Nos. 3,331,776; 3,381,022; and 3,522,179.
  • the alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succinimides described above.
  • Suitable alkenyl succinic ester-amides for forming the phosphorylated ashless dispersant are described for example in U.S. Pat. Nos. 3,184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540.
  • Hydrocarbyl polyamine dispersants that can be phosphorylated are generally produced by reacting an aliphatic or alicyclic halide (or mixture thereof) containing an average of at least about 40 carbon atoms with one or more amines, preferably polyalkylene polyamines. Examples of such hydrocarbyl polyamine dispersants are described in U.S. Pat. Nos. 3,275,554; 3,394,576; 3,438,757; 3,454,555; 3,565,804; 3,671,511; and 3,821,302.
  • the hydrocarbyl-substituted polyamines are high molecular weight hydrocarbyl-N-substituted polyamines containing basic nitrogen in the molecule.
  • the hydrocarbyl group typically has a number average molecular weight in the range of about 750-10,000 as determined by GPC, more usually in the range of about 1,000-5,000, and is derived from a suitable polyolefin.
  • Preferred hydrocarbyl-substituted amines or polyamines are prepared from polyisobutenyl chlorides and polyamines having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
  • Mannich polyamine dispersants which can be utilized in forming the phosphorylated ashless dispersant is a reaction product of an alkyl phenol, typically having a long chain alkyl substituent on the ring, with one or more aliphatic aldehydes containing from 1 to about 7 carbon atoms (especially formaldehyde and derivatives thereof), and polyamines (especially polyalkylene polyamines). Examples of Mannich condensation products, and methods for their production are described in U.S. Pat. Nos.
  • the preferred hydrocarbon sources for preparation of the Mannich polyamine dispersants are those derived from substantially saturated petroleum fractions and olefin polymers, preferably polymers of mono-olefins having from 2 to about 6 carbon atoms.
  • the hydrocarbon source generally contains at least about 40 and preferably at least about 50 carbon atoms to provide substantial oil solubility to the dispersant.
  • the olefin polymers having a GPC number average molecular weight between about 600 and 5,000 are preferred for reasons of easy reactivity and low cost. However, polymers of higher molecular weight can also be used.
  • Especially suitable hydrocarbon sources are isobutylene polymers.
  • the preferred Mannich base dispersants for this use are Mannich base ashless dispersants formed by condensing about one molar proportion of long chain hydrocarbon-substituted phenol with from about 1 to 2.5 moles of formaldehyde and from about 0.5 to 2 moles of polyalkylene polyamine.
  • Polymeric polyamine dispersants suitable for preparing phosphorylated ashless dispersants are polymers containing basic amine groups and oil solubilizing groups (for example, pendant alkyl groups having at least about 8 carbon atoms). Such materials are illustrated by interpolymers formed from various monomers such as decyl methacrylate, vinyl decyl ether or relatively high molecular weight olefins, with aminoalkyl acrylates and aminoalkyl acrylamides. Examples of polymeric polyamine dispersants are set forth in U.S. Pat. Nos. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
  • the dispersants or the phosphorus-containing dispersants of the present invention are also boronated.
  • the amount of phosphorylated ashless dispersant on an "active ingredient basis" is generally within the range of about 0.5 to about 7.5 weight percent (wt%), typically within the range of about 0.5 to 6.5 wt%, preferably within the range of about 0.5 to about 5.5 wt%, and most preferably within the range of about 1.0 to about 4.5 wt%.
  • an optional component of the present invention is a dispersant having a nitrogen to phosphorus mass ratio between about 3:1 and about 10:1.
  • the dispersant of the preferred embodiment can be prepared in at least two ways. In one method, an ashless dispersant is phosphorylated to such a degree that the nitrogen to phosphorus mass ratio between about 3:1 and about 10:1. In another embodiment, a phosphorylated dispersant and a non-phosphorylated dispersant are blended together such that the total nitrogen to phosphorus mass ratio of the dispersant is between about 3:1 and about 10:1.
  • the dispersant is preferably present in the final fluid in an amount of about 1.00% to about 10.00% by weight, more preferably from about 1.00 weight % to about 7.00 weight %, most preferably about 3-6 weight %.
  • compositions of the present invention contain at least one amine-based friction modifier, and most preferably a mixture of amine-based friction modifiers. These may be in combination with other friction modifiers as well.
  • the amine-based friction modifiers typically include such compounds as fatty amines or ethoxylated fatty amines, ethoxylated aliphatic ether amines, and fatty tertiary amines.
  • Other suitable nitrogen containing friction modifiers include fatty imidazolines, aliphatic fatty acid amides, and the like.
  • Various other known compounds which are suitable as friction modifiers include aliphatic carboxylic acids, glycerol esters, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, and aliphatic thiophosphates.
  • the aliphatic group may contain above about eight carbon atoms so as to render the compound suitably oil soluble.
  • Suitable friction modifiers also include metal salts of fatty acids.
  • Preferred cations are zinc, magnesium, calcium, barium, and sodium and any alkaline, or alkaline earth metals may, be used.
  • the salts may be overbased by including and excess of cations per equivalent of amine. The excess cations are then treated with carbon dioxide to form the carbonate.
  • the metal salts are prepared by reacting a suitable salt with the acid to form the salt, and where appropriate adding carbon dioxide to the reaction mixture to form the carbonate of any cation beyond that needed to form the salt.
  • a preferred friction modifier is zinc oleate.
  • aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia or other primary amines.
  • One preferred group of friction modifiers is comprised of the N-aliphatic hydrocarbyl-substituted diethanol amines in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms.
  • Some commercially available friction modifiers which are suitable in the practice of the invention are the Armeen® series of primary amines (12D,16D, 18D, O, OD, OL, OLD, C, CD, S, SD, T, TD, HT, and HTD); secondary amines (2C, 2T, 2HT, 2-18); tertiary monoalkyl amines (DM12D, DM16D, DM18D, DMOD, DMCD, DMSD, DMTD, DMHTD); tertiary dialkyl amines (M2C, M2HT); tertiary trialkyl amines (3-12, 3-16); diamines, under the tradename Duomeen® (C, CD, T, TTM, OL, LT-4, S); triamines, under the tradename Triameen® T; tetramines, under the tradename Tetrameen® T; ethoxylated amines, under the tradename Ethomeen® (C-12, C
  • alkanolamides derived from C 12 -C 18 fatty acids, e.g. cocoamide and tallowamide.
  • Commercial examples of these alkanolamides include Schercomid SL-ML (lauramide diethanolamine), and Schercomid SOA-E, a C 18 -amide, each available from Scher Chemicals, Inc, New Jersey. Schercomid SL-ML is especially preferred.
  • a particularly preferred friction modifier system is composed of a combination of at least one N-aliphatic hydrocarbyl-substituted diethanolamine and at least one N-aliphatic hydrocarbyl-substituted trimethylene diamine in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms. Further details concerning this friction modifier system are set forth in U.S. Pat. Nos. 5,372,735 and 5,441,656, incorporated herein by reference.
  • Another particularly preferred friction modifier system is based on the combination of (i) at least one di(hydroxyalkyl) aliphatic tertiary amine in which the hydroxyalkyl groups, being the same or different, each contain from 2 to about 4 carbon atoms, and in which the aliphatic group is an acyclic hydrocarbyl group containing from about 10 to about 25 carbon atoms, and (ii) at least one hydroxyalkyl aliphatic imidazoline in which the hydroxyalkyl group contains from 2 to about 4 carbon atoms, and in which the aliphatic group is an acyclic hydrocarbyl group containing from about 10 to about 25 carbon atoms. Further details concerning this friction modifier system are set forth in U.S. Pat. No. 5,344,579, incorporated herein by reference.
  • Component (i) the di(hydroxyalkyl) aliphatic tertiary amine, has a nitrogen atom to which are bonded two hydroxyalkyl groups and one non-cyclic aliphatic hydrocarbyl group having 10 to 25 carbon atoms, and preferably 13 to 19 carbon atoms.
  • the hydroxyalkyl groups of these tertiary amines can be the same or different, but each contains from 2 to 4 carbon atoms.
  • the hydroxyl groups can be in any position in the hydroxyalkyl groups, but preferably are in the ⁇ -position.
  • the two hydroxyalkyl groups in component (i) are the same, and most preferably are 2-hydroxyethyl groups.
  • the aliphatic group of these tertiary amines can be straight or branched chain and it can be saturated or olefinically unsaturated and if unsaturated, it typically contains from one to three olefinic double bonds.
  • Component (i) can have a single type of aliphatic group or it can comprise a mixture of compounds having different aliphatic groups in which the average number of carbon atoms falls within the foregoing range of from 10 to 25 carbon atoms.
  • Another set of friction modifiers which is suitable for practice within the scope of the present invention includes: 1) at least one dihydroxy alkyl aliphatic tertiary amine (e.g., alkyl C 12 -C 18 and cyclic hydrocarbyl); and 2) at least one aliphatic fatty alkanol amide in which the aliphatic group is an acyclic hydrocarbyl group containing from 12 to 18 carbon atoms.
  • the aliphatic fatty alkanol is preferably a dihydroxy alkyl.
  • component (i) can be a single compound or a mixture of compounds meeting the structural criteria described above.
  • hydroxyalkyl aliphatic imidazolines, component (ii), suitable for use in the practice of this invention are characterized by having in the 1-position on the imidazoline ring a hydroxyalkyl group that contains from 2 to 4 carbon atoms, and by having in the adjacent 2-position on the ring a non-cyclic hydrocarbyl group containing 10 to 25 carbon atoms. While the hydroxyl group of the hydroxyalkyl group can be in any position thereof, it preferably is on the ⁇ -carbon atom, such as 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl.
  • the aliphatic group is a saturated or olefinically unsaturated hydrocarbyl group, and when olefinically unsaturated, the aliphatic group may contain one, two or three such double bonds.
  • Component (ii) may be a single substantially pure compound or it may be a mixture of compounds in which the aliphatic group has an average of from 10 to 25 carbon atoms.
  • the aliphatic group has 15 to 19 carbon atoms, or an average of 15 to 19 carbon atoms.
  • the aliphatic group has, or averages, 17 carbon atoms.
  • the aliphatic group(s) may be straight or branched chain groups, with substantially straight chain groups being preferred.
  • a particularly preferred compound is 1-hydroxyethyl-2-heptadecenyl imidazoline.
  • a commercially available imidazoline based friction modifier essentially suitable for use as ii) in the invention is Unamine O, available from Lonza Chemicals.
  • component (ii) can be a single compound or a mixture of compounds meeting the structural criteria described above.
  • the fully formulated final compositions of this invention will optionally contain up to about 1.25 wt% on an active ingredient basis, and preferably from about 0.005 to about 1.10 wt% on an active ingredient basis of one or more friction modifiers, most preferably about 0.005 to about 1.00 wt %.
  • compositions according to the present invention may also be present in compositions according to the present invention.
  • compositions of the present invention may include one or more antioxidants, for example, one or more phenolic antioxidants, hindered phenolic antioxidants, additional sulfurized olefins, aromatic amine antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants (e.g. organic phosphites), and mixtures thereof.
  • one or more phenolic antioxidants for example, one or more phenolic antioxidants, hindered phenolic antioxidants, additional sulfurized olefins, aromatic amine antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants (e.g. organic phosphites), and mixtures thereof.
  • antioxidants for example, one or more phenolic antioxidants, hindered phenolic antioxidants, additional sulfurized olefins, aromatic amine antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-
  • Suitable exemplary compounds include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), mixed methylene-bridged polyalkyl phenols, 4,4'-thiobis(2-methyl-6-tert-butylphenol), N,N'-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenyl amine, phenyl- ⁇ -naphthyl amine, and phenyl- ⁇ -naphthyl amine.
  • Especially preferred antioxidants include diphenyl amine derived antioxidants; such as Naugalube® 438-L.
  • aromatic secondary monoamines include diphenylamine, alkyl diphenylamines containing 1 to 2 alkyl substituents each having up to about 16 carbon atoms, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, alkyl- or aralkylsubstituted phenyl- ⁇ -naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkyl- or aralkyl-substituted phenyl- ⁇ -naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkylated p-phenylene diamines available from Goodyear under the tradename "Wingstay 100" and from Uniroyal,
  • the preferred type of aromatic amine antioxidant is that embodied in the commercial product Naugalube 483L is an alkylated diphenylamine of the general formula : R 1 --C 6 H 4 --NH--C 6 H 4 --R 2 wherein R 1 is an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms) and R 2 is a hydrogen atom or an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms). Most preferably, R 1 and R 2 are the same. Particularly preferred is a nonylated diphenyl amine containing 4,4'-dinonylated diphenyl amine; a bis(4-nonylphenyl)(amine) wherein the nonyl groups are branched.
  • suitable compounds include ortho-alkylated phenolic compounds, e.g. 2-tert-butylphenol, 2,6-di-tertbutylphenol, 4-methyl-2,6-di-tertbutylphenol, 2,4,6-tri-tertbutylphenol, and various analogs and homologs or mixtures thereof; one or more partially sulfurized phenolic compounds as described in US Patent 6,096,695, the disclosure of which is incorporated herein by reference; methylene-bridged alkylphenols as described in U.S. Pat. No. 3,211,652, the disclosure of which is incorporated herein by reference.
  • Antioxidants may be optionally included in the fully formulated final inventive lubricating composition at from about 0.00 to about 5.00 weight percent, more preferably from about 0.01 weight % to about 1.00 weight %, most preferably about 0.05 wt % to about 0.50 wt %.
  • the automatic transmission fluids of the present invention may further include anti-wear/extreme pressure additives.
  • the remainder of the phosphorus content is preferably supplied by inclusion in the composition of one or more phosphorus-containing esters or acid-esters such as oil-soluble organic phosphites, oil-soluble organic acid phosphites, oil-soluble organic phosphates, oil-soluble organic acid phosphates, oil-soluble phosphoramidates.
  • Examples include trihydrocarbyl phosphates, trihydrocarbyl phosphites, dihydrocarbyl phosphates, dihydrocarbyl phosphonates or dihydrocarbyl phosphites or mixtures thereof, monohydrocarbyl phosphates, monohydrocarbyl phosphites, and mixtures of any two or more of the foregoing.
  • Oil-soluble amine salts of organic acid phosphates are a preferred category of auxiliary phosphorus-containing additives for use in the fluids of this invention. Sulfur-containing analogs of any of the foregoing compounds can also be used, but are less preferred.
  • Suitable commercially available auxiliary phosphorus additives include amine phosphate antiwear/extreme pressure agents, available from Ciba-Geigy Corporation as Irgalube® 349 and R.T. Vanderbilt Inc. as Vanlube® 672.
  • sulfurized fatty acid esters e.g. the Sul-Perm® brand of sulfurized fatty acid esters from Keil Chemical, and sulfurized dithiocarbamates, and alkyl thiadiazoles such as HiTEC® 4312 and 4313, available from Ethyl Corporation, Richmond, Virginia.
  • the extreme pressure/anti wear additive is preferably present in the final fully-formulated fluid in an amount of from 0.00 to about 1.00 weight %, more preferably from about 0.01 to about 0.50 weight %.
  • compositions of the present invention optionally, but preferably, contain a viscosity index improver (VII).
  • VI viscosity index improver
  • Preferred VIIs include, but are not limited to, olefin copolymer VIIs, polyalkylmethacrylate VIIs and styrene-maleic ester VIIs. Of these, polyalkylmethacrylate VIIs are particularly preferred.
  • the viscosity index improver is supplied in the form of a solution in an inert solvent, typically a mineral oil solvent, which usually is a severely refined mineral oil.
  • the viscosity index improver solution as received often will have a boiling point above 200°C, and a specific gravity of less than 1 at 25 °C.
  • the viscosity index improver will have sufficient shear stability such that the finished composition possesses a kinematic viscosity of at least 5, and more preferably at least 6.8, cSt at 100 °C after 40 cycles in the FISST (Fuel Injector Shear Stability Test) of ASTM D-5275.
  • FISST Full Injector Shear Stability Test
  • the VII in the present invention will also preferably have less than 5% shear loss on the tapered roller bearing test.
  • the finished fluid compositions of this invention will normally contain in the range of about 0 to about 15 wt% of the polymeric viscosity index improver. Small departures from this range may be resorted to as necessary or desirable in any given situation.
  • Suitable materials for use as component (F) include styrene-maleic ester VIIs such as LUBRIZOL® 3702, LUBRIZOL®3706 and LUBRIZOL®3715 available from The Lubrizol Corporation; polyalkylmethacrylate VIIs such as those available from R ⁇ HM GmbH (Darmstadt, Germany) under the trade designations: VISCOPLEX® 5543, VISCOPLEX® 5548, VISCOPLEX® 5549, VISCOPLEX® 5550, VISCOPLEX® 5551 and VISCOPLEX® 5151, from Rohm & Haas Company (Philadelphia, Pennsylvania) under the trade designations ACRYLOID® 1277, ACRYLOID® 1265 and ACRYLOID® 1269, and from Ethyl Corporation (Richmond, Virginia) under the trade designation HiTEC® 5710 viscosity index improver; and olefin copolymer VIIs such as HiTEC® 5747 VII, HiTEC® 5751 VII, HiTEC® 5770 VII
  • the viscosity index improver will be provided as a hydrocarbon solution having a polymer content in the range of from about 25 to about 80 wt% and a nitrogen content in the range of about 0 to about 0.5 wt%.
  • Such products preferably exhibit a permanent shear stability index (a PSSI value) using ASTM test method D-3945A of no higher than about 75, preferably 50 or less, and most preferably 35 or less.
  • a dispersant polymethacrylate viscosity index improver such as HiTEC® 5738, or a non dispersant polymethacrylate viscosity index improver such as HiTEC®5739, both products of Ethyl Corporation, Richmond Virginia, or a mixture of dispersant and non-dispersant viscosity index improvers.
  • an ultra high shear stable dispersant polymethacrylate viscosity index improver such as HITEC 5769, also a product of Ethyl Corporation, Richmond, Virginia.
  • the viscosity index improver may be present in an amount of from 0-25% by weight, preferably from 5-20% by weight.
  • alkyl polyoxyalkylene ethers such as Mazawet® 77, C-8 acids such as Neofat® 8, oxyalkyl amines such as Tomah PA-14, 3-decyloxypropylamine, and polyoxypropylene-polyoxyethylene block copolymers such as Pluronic® L-81.
  • Anti-rust agents are especially preferred.
  • Anti-rust agents are preferably used in low quantities, e.g. less than about 0.2 wt %, preferably from about 0.01 to about 0.15 weight %.
  • Anti-foam/Surfactant agents may also be included in a fluid according to the present invention.
  • Various agents are known for such use.
  • silicone fluids such as 4% DCF. Mixtures of anti-foam agents are especially preferred.
  • anti foam agents are generally present in small amounts, from about 0.00 - 0.10 weight %, more preferably between about 0.02-0.07 wt %, most preferably about 0.05 wt %.
  • a colorant to the fluid to give it a unique character which is detectable.
  • azo class dyes are used, such as C.I. Solvent Red 24 or C.I. Solvent Red 164, as set forth in the "Colour Index" of the American Association of Textile Chemists and Colorists and the Society of Dyers and Colourists (U.K.) which is incorporated herein by reference.
  • Automate Red Dye is especially preferred.
  • Dye is present in a very minimal amount, usually less than 400 ppm, preferably between about 200-300 ppm in the finished oil.
  • a suitable carrier diluent is added to ease blending, solubilizing, and transporting the additive package.
  • the diluent oil needs to be compatible with the base oil and the additive package.
  • the diluent is present in the concentrate in an amount of between 5-20%, although it can vary widely with application. Generally speaking, less diluent is preferable as it lowers transportation costs and treat rates.
  • a suitable diluent is a process oil of lubricating viscosity.
  • inventive composition is to be prepared as a concentrate, then base oil may be omitted and an appropriate adjustment made in the weight % of each of the above optional and mandatory ingredients to prepare a suitable concentrate, taking care that solubility and compatibility is maintained. However, if a fully formulated fluid is to be prepared, then base oil is a mandatory component.
  • the base oils used in forming the automatic transmission fluids of this invention can be any suitable natural or synthetic oil having the necessary viscosity properties for this usage.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil etc.), liquid petroleum oils and hydrorefined, severely hydrotreated, iso-dewaxed, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • the synthetic lubricating oils suitable for use in this invention include one of any number of commonly used synthetic hydrocarbon oils, which include, but are not limited to, poly-alpha-olefins, synthetic esters, alkylated aromatics, alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification etc., esters of dicarboxylic acids and silicon-based oils.
  • the base oil may be composed entirely of a natural oil such as mineral oil of suitable viscosity or it may be composed entirely of a synthetic oil such as a poly-alpha-olefin oligomer of suitable viscosity.
  • the base oil may be a blend of natural and/or synthetic base oils provided that the blend has the requisite properties for use in the formation of an automatic transmission fluid.
  • the base oil should have a kinematic viscosity in the range of 3 to 8 centistokes (cSt) at 100 °C.
  • Preferred automatic transmission fluids used in the practice of this invention can be formulated without a viscosity index improver so as to possess a kinematic viscosity of at least 3.0 cSt at 100°C and a Brookfield viscosity of no more than 20,000 cP at -40 °C, or formulated using a viscosity index improver so as to possess a kinematic viscosity of at least 6.8 cSt at 100 °C and a Brookfield viscosity of no more than 20,000 cP at -40 °C.
  • Suitable base stock oil includes, preferably, Group I, II, and III base oils, as are known to those of skill in the art. In certain instances, usually depending on the final use of the lubricant composition according to the present invention, Group I is preferred, and in other instances, Group II and III are preferred.
  • Group I base stocks contain less than 90% saturates (as determined by ASTM D 2007) and/or greater than 0.03 percent sulfur (as determined by ASTM D 2622, D 4294, D 4927, or D 3120) and have a viscosity index greater than or equal to 80 and less than 120 (as determined by ASTM D 2270).
  • Group II base stocks contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulfur and have a viscosity index greater than 80 and less than 120 using the above noted test methods.
  • Group II + oils may also be used. These are oils which have a VI at the high end of the VI spectrum, e.g. about 120.
  • Group III base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 % sulfur and have a viscosity index greater than or equal to 120 using the tests noted above.
  • the transmission fluid contains less than 5% poly-alpha-olefins (PAO) and is more preferably PAO free.
  • PAO poly-alpha-olefins
  • the automatic transmission fluids of the present invention may further include seal swell agents.
  • Seal swell agents such as esters, adipates, sebacates, azealates, phthalates, sulfones, alcohols, alkylbenzenes, substituted sulfolanes, aromatics, or mineral oils cause swelling of elastomeric materials used as seals in engines and automatic transmissions.
  • Alcohol-type seal swell agents are generally low volatility linear alkyl alcohols, such as decyl alcohol, tridecyl alcohol and tetradecyl alcohol.
  • Alkylbenzenes useful as seal swell agents include dodecylbenzenes, tetradecylbenzenes, dinonyl-benzenes, di(2-ethylhexyl)benzene, and the like.
  • Substituted sulfolanes are likewise useful as seal swell agents in compositions according to the present invention.
  • Mineral oils useful as seal swell agents in the present invention include low viscosity mineral oils with high naphthenic or aromatic content.
  • Aromatic seal swell agents include the commercially available Exxon Aromatic 200 ND seal swell agent.
  • mineral oil seal swell agents include Exxon® Necton®-37 (FN 1380) and Exxon® Mineral Seal Oil (FN 3200).
  • a seal swell agent When used in the ATF of the present invention, a seal swell agent will typically comprise from about 1 to about 30 wt. %, preferably from about 1 to about 20 wt. %, most preferably from about 1 to about 10 wt. %, based on the total weight of ATF.
  • the automatic transmission fluids of the present invention may further include additional corrosion inhibitors (it should be noted that some of the earlier mentioned components, e.g. monoalkyl and dialkyl thiadiazole each have copper corrosion inhibition properties).
  • additional corrosion inhibitors of copper corrosion include ether amines, polyethoxylated compounds such as ethoxylated amines and ethoxylated alcohols, imidazolines, and the like.
  • Thiazoles, triazoles and thiadiazoles may also be used in the present invention.
  • Examples include benzotriazole; tolyltriazole; octyltriazole; decyltriazole; dodecyltriazole; 2-mercaptobenzothiazole; 2,5-dimercapto-1,3,4-thiadiazole; 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles; and 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles.
  • the preferred compounds are the 1,3,4-thiadiazoles, especially the 2-hydrocarbyldithio-5-mercapto-1,3,4-dithiadiazoles, a number of which are available as articles of commerce. These may be present in an amount of from 0.00 to 0.50 weight percent, more preferably from about 0.01 to about 0.10 weight percent, based on the final formulation.
  • any of the foregoing optional additives it is important to ensure that the selected component(s) is/are soluble or stably dispersible in the additive package and finished ATF composition, are compatible with the other components of the composition, and do not interfere significantly with the performance properties of the composition, such as the friction, viscosity and/or shear stability properties, needed or at least desired in the overall finished composition.
  • the ancillary additive components are employed in the oils in minor amounts sufficient to improve the performance characteristics and properties of the base fluid.
  • the amounts will thus vary in accordance with such factors as the viscosity characteristics of the base fluid employed, the viscosity characteristics desired in the finished fluid, the service conditions for which the finished fluid is intended, and the performance characteristics desired in the finished fluid.
  • the individual components employed can be separately blended into the base fluid or can be blended therein in various subcombinations, if desired. Ordinarily, the particular sequence of such blending steps is not critical. Moreover, such components can be blended in the form of separate solutions in a diluent. It is preferable, however, to blend the additive components used in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
  • Additive concentrates can thus be formulated to contain all of the additive components and if desired, some of the base oil component, in amounts proportioned to yield finished fluid blends consistent with the concentrations described above.
  • the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate.
  • concentrates containing up to about 50% by weight of one or more diluents or solvents can be used, provided the solvents are not present in amounts that interfere with the low and high temperature and flash point characteristics and the performance of the finished power transmission fluid composition.
  • the additive components utilized pursuant to this invention should be selected and proportioned such that an additive concentrate or package formulated from such components will have a flash point of 170 °C or above, and preferably a flash point of at least 180 °C, using the ASTM D-92 test procedure.
  • the finished fluid or concentrate should be essentially free of phenolic antioxidants and sulfurized fats.
  • compositions suitable for use in the practice of this invention are presented in the following Examples, wherein all parts and percentages are by weight unless specified otherwise.
  • the fluids prepared in the Examples were then subjected to testing under commonly known tests, including the low speed SAE #2 rig, under the conditions noted, and the GM plate clutch friction test (GM performance specification GM 6417 M, April 1997) run according to Dexron® III procedures. Briefly, this test involves engaging the clutch at the rate of four cycles per minute for 100 hours (i.e., 24,000 cycles) at 135 degrees C.
  • the DEXRON® III Band Clutch Test limit for the mid-point torque is 185-220 Nm.
  • GM-6297-M The GM Dexron III Cycling Test (GM-6297-M), revised April 1993; corresponding to the Ford Mercon V Friction Durability Test (Dexron 5 Specification 3.9, Revised Jul 1, 1996 and October 1, 1998 which sets limits on shift times for 20,000 shift cycles. Shifting from 1st to 2nd gear, 0.30-0.75 seconds; from 2nd to 3rd gear 0.30 to 0.75 sec.
  • the FZG wear test conducted in the FZG gear rig test machine.
  • IP Institute of Petroleum 334/79, which is incorporated herein by reference, measures lubricity, and in the test, two steel spin gears are rotated together for a series of 75 minute stages. The relative torque between the gears is increased by a fixed amount after each stage and the gears are run together for a given period after which they are examined for wear or damage. The result of the test is quoted in terms of the final pass stage and the first fail stage.
  • the test is technically equal to ASTM D 5182-97. This test can be conducted at selected temperatures, nominally 90 degrees C and 150 degrees C.
  • compositions according to the present invention resisted oxidation for at least 500 hours.
  • a composition according to the present invention has excellent initial anti-shudder properties, excellent friction durability, extended anti-shudder performance, and oxidation resistance.
  • the fluid according to the present invention has a level tail without the characteristic rooster tail which indicates shudder or stick-slip as seen in Examples 1 and 2.
  • Figure 5 illustrated the degradation in performance of a fluid of comparative example 2 (not of the invention) under the ECCC friction durability test run on the SAE #2 low speed rig. After about 72 hours, a considerable degradation is seen. Thereafter, the vehicle can be expected to shudder.
  • Figure 6 illustrates the ECCC friction durability results on the SAE #2 low speed rig for Example 2.
  • the coefficient of friction has dropped, after 120 hours, to between 0.130 and 0.120, which would result in the loss of torque and fuel economy in a vehicle.

Abstract

Automatic transmission fluids are described which contain at least 0,1wt% of a metal-containing detergent, a dispersant, and a mixture of friction modifiers. The transmission fluids according to the present invention exhibit excellent initial anti shudder properties, excellent anti-shudder durability, and excellent friction durability.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • There are no related applications.
  • STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
  • This research was not sponsored by any entity of the Federal Government.
  • BACKGROUND OF THE INVENTION 1. Field of the Invention
  • This invention relates to oil-based automatic transmission fluid compositions having excellent slip-stick characteristics, anti-shudder performance, and friction durability. More specifically, a preferred aspect of the invention relates to a use of the automatic transmission fluid in electronically controlled converter clutch (ECCC) applications.
  • 2. Description of the Prior Art
  • US Patent 5,578,236, to Ethyl Corporation discloses a power transmission fluid with enhanced performance characteristics. The power transmission fluid composition disclosed therein has, inter alia, an oil-soluble boron content of about 0.001 to about 0.1%, an oil soluble phosphorus content of about 0.005 to about 0.2%, and an oil soluble metal additive content of from 0 to about 100 ppm.
  • The composition of the '236 patent comprises at least about 50 weight % hydrotreated mineral oils in the range of about 55N to about 125N, about 5 to 40 wt% of hydrogenated poly alpha olefin oligomer having a viscosity of about 2 to about 6 cSt at 100 ° C, about 5 to about 20 wt % of an acrylic viscosity index improver, a seal swell agent, an ashless dispersant, an oil soluble friction modifier, and an inhibitor selected from foam, copper corrosion (including thiadiazoles), rust, and oxidation inhibitors. The finished composition has a Brookfield viscosity of 13,000 cP or less at - 40 ° C, an ASTM D-4683 viscosity of at least 2.6 mPa.s at 150 ° C, and a viscosity of at least 6.8 cSt at 100° C after 40 cycles in the FISST of ASTM D-5275. However, the compositions disclosed are preferably devoid of sulfurized components.
  • US Patent 5,441,656, also to Ethyl Corporation, discloses an automatic transmission fluid for overcoming shudder problems in continuous slip torque converter clutches in automatic transmissions. The automatic transmission fluid ("ATF") of the '656 patent includes, among other restrictions, a friction modifier content which contains an N-aliphatic hydrocarbyl substituted diethanolamine in which the N-aliphatic hydrocarbyl substituent having in the range of about 14 to about 40 carbon atoms, and an N-aliphatic hydrocarbyl substituted trimethylene diamine in which the N-aliphatic hydrocarbyl substituent is at least one straight chain aliphatic hydrocarbyl group having in the range of about 14 to about 20 carbon atoms. Conventional copper corrosion inhibitors (including thiadiazoles) and other optional (e.g. lubricity, dye, pour point depressant, etc.) components may be present.
  • U.S. Patent Nos. 5,344,579; 5,372,735; and 5,578,236 disclose automatic transmission fluid compositions which exhibit good anti-shudder properties.
  • Other U.S. Patents which disclose various automatic transmission fluids include 4,795,583; 4,855,074; 4,857,214; 5,089,156; 5,126,064; 5,164,103; 5,171,466; 5,198,133; 5,256,324; 5,360,562; 5,387,346; 5,387,352; 5,389,273; 5,439,606; 5,505,868; 5,652,201; 5,703,023; 5,817,605; 5,851,962; 5,891,786; and 5,972,851. Each of the above is incorporated by reference.
  • These references; however, fail to teach or suggest the combination of components of the present invention, including the combination of at least 0.10 wt % of a metal-containing detergent, a dispersant, and a friction modifier system including a mixture of at least two different friction modifiers. A preferred mixture of friction modifiers is a mixture of an ethoxylated amine and an imidazoline. Such a combination gives a friction durability of at least 200 hours as measured by the low speed ECCC friction durability test. It also gives a good balance of torque capacity, durability, initial shudder free performance (during a break in period) and continues to have a robust anti shudder durability over the lifetime of the fluid.
  • Commercially, it is known to add various additive packages to automatic transmission fluid, including, among other things, extreme pressure agents, antiwear agents, antioxidant systems, corrosion inhibitor systems, metal deactivators, anti-rust agents, friction modifiers, dispersants, detergents, anti-foam agents, and viscosity index improvers. However, not all additives interact predictably or well with one another.
  • BRIEF SUMMARY OF THE INVENTION
  • The present invention relates to the improvement of friction durability, anti-shudder performance, and slip-stick performance by the inclusion into a final formulated automatic transmission fluid of a metal-containing detergent, a dispersant, and a friction modifier system including an ethoxylated amine and an imidazoline.
  • Other optional components, e.g. anti-rust agents, corrosion inhibitors, additional friction modifiers, antioxidants, anti foam agents, extreme pressure agents, additional dispersants or detergents, and viscosity index improvers, may also be included. The fully formulated transmission fluid composition provides enhanced performance, especially for ECCC automatic transmissions
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 is a graphical illustration of the friction durability of a composition (Example 3) according to the present invention measured by coefficient of friction and speed.
  • Figure 2 is a graphical illustration of the friction durability of a composition according to the present invention (Example 3) measured by ratio of coefficients of friction and time.
  • Figure 3 is a graphical illustration of the extended duration plate clutch friction test results of a composition according to the present invention (Example 3) compared with two compositions not of the invention (Examples 1 and 2).
  • Figure 4 is a graphical illustration of the initial shudder durability of a composition according to the present invention (Example 3) and two comparative examples not of the invention (Examples 1 and 2).
  • Figure 5 is a graphical representation of the ECCC friction durability of a comparative example (Example 2), measured by hours to negative slope.
  • Figure 6 is a graphical representation of an ECCC friction durability test, measured by coefficient of friction against speed, for an example not of the present invention (Example 2).
  • DETAILED DESCRIPTION OF THE INVENTION
  • Vehicles meeting the stringent demands of consumers today require durability and performance in all of the vehicular systems. One of the most important systems is the power transmission system ("transmission") which transmits the power generated by the automobile engine to the wheels. It being one of the most complex systems in the vehicle, it is also one of the most costly to diagnose, repair, or replace. The transmission usually includes, inter alia, a clutch with plates, a torque converter, and a plurality of gears to alter the power delivered to the wheels by changing the gear ratio. It may also include a wet clutch.
  • Discriminating consumers primarily desire high performance, low maintenance (high mileage between servicing), and extended life expectancy. However, with the advent of new transmission technologies, old standards of performance which were previously met with approval are now becoming unacceptable.
  • For example, there is worldwide activity by the automobile manufacturers to develop automatic transmissions incorporating various electronically controlled converter clutch (ECCC) designs. These developments are being driven by the anticipated increase in Corporate Average Fuel Economy (CAFE) requirements in the U.S.A. The ECCC design allows increases in fuel economy to be gained.
  • The advent of ECCC transmissions as well as vehicles equipped with a continuously variable transmission (CVT) and advances in aerodynamic body design result in passenger cars with smaller transmissions which tend to operate with higher energy densities and higher operating temperatures. Such changes have challenged lubricant suppliers to formulate automatic transmission fluids with new and unique performance characteristics including higher torque capacity and friction durability.
  • As a result, many original equipment manufacturers (OEMs) are looking for automatic transmission fluids with frictional characteristics capable of meeting or exceeding the requirements of ECCC, CVT, and other designs while retaining sufficient anti-wear, anti-shudder, and friction durability performance.
  • A need exists for an effective way of increasing the friction durability, and hence the service life, of automatic transmission fluids, especially to meet the needs of vehicles with the new ECCC or CVT transmissions.
  • This invention thus provides an automatic transmission fluid that exhibits excellent initial anti shudder performance, anti-shudder durability, and friction durability.
  • This invention also provides an automatic transmission fluid capable of passing the GM 3T40 Plate Friction and the DaimlerChrysler Friction Durability test.
  • The metal-containing detergent includes, by way of example, calcium-containing detergents such as calcium sulfonates,, the dispersant includes by way of example succinimide-type dispersants, which may be boronated or phosphorylated, and the friction modifier system includes, also by way of example, an ethoxylated amine and an imidazoline.
  • In one embodiment, the fluids of the present invention are used in formulating automatic transmission fluids which exhibit good frictional characteristics. In another embodiment, the fluids of the present invention are used in formulating automatic transmission fluids which exhibit excellent initial anti-shudder performance, and outstanding friction durability in the ECCC Friction durability test, as measured by the low speed SAE#2 friction rig.
  • As is well known in the art, the friction durability of an ATF is assessed through the use of an SAE #2 friction test machine. This machine simulates the high-speed engagement of a clutch by using the clutch as a brake, thereby absorbing a specified amount of energy. The energy of the system is chosen to be equivalent to the energy absorbed by the clutch in completing one shift in the actual vehicle application. The machine uses a specified engagement speed, normally 3600 rpm, and a calculated inertia to provide the required amount of energy to the test clutch and fluid. The clutch is lubricated by the fluid being evaluated, and each deceleration (i.e., braking) of the system is termed one cycle. To evaluate friction durability many cycles are run consecutively. Increasing emphasis on friction durability by original equipment manufacturers (OEM's) has caused the total number of cycles required to demonstrate satisfactory friction durability to increase from several hundred in the 1980's to more than 30,000 in some proposed specifications.
  • There are two methods of assessing improved friction durability. One is to maintain certain friction characteristics over a longer period of time (cycles). The second is to allow less change in each friction parameter over the same number of cycles. Both methods provide indications that the vehicle shift characteristics will be consistent over a longer number of miles.
  • Said methods comprise adding to, and operating in, an automatic transmission an automatic transmission fluid comprising (1) a major amount of a base oil and (2) a minor amount of an additive composition which comprises, as essential components at least Component (A); Component (B); and Component (C) as described below.
  • Although the Components above and in the below list are described occasionally with reference to a function, that function may be one of other functions served by the same component and should not be construed as a mandatory limiting function.
  • MANDATORY COMPONENTS Component (A) Detergent
  • Relatively large amounts of metal-containing detergents, such as calcium sulfurized phenates, magnesium phenates, calcium sulfonates, and magnesium phenates are used in formulations according to the present invention. Suitable metals include, but are not limited to, those found in Group 2A of the periodic table.
  • It has heretofore been conventional to use such detergents in far lesser quantities, e.g. no more than about 250 ppm of metal, usually no more than about 100 ppm of metal, and most commonly no more than about 50 ppm of metal.
  • However, in the practice of the present invention, the amount of detergent is preferably elevated to a high degree, e.g. above 0.10 wt% and up to about 1.50 wt % for example, above 0.15 wt% to 1.50 wt% preferably between about 0.15 wt% and about 1.00 wt%, most preferably about 0.15-0.50 wt%.
  • While not wishing to be bound by theory, it is surmised that these high levels of detergent act to increase anti-shudder durability by limiting the thermal and oxidative degradation of surface-active components.
  • These sulfurized phenates may be salts containing a stoichiometric amount of calcium, and also generally having a total base number (TBN) of not more than about 300 mg KOH/gram. One commercially available calcium phenate which is suitable for the practice of the instant invention is OLOA 216C, a calcium hydroxide salt of a sulfurized alkyl phenate having a nominal TBN of about 150, available from Oronite Division of Chevron Chemical Co. HiTEC® 614, a neutral calcium sulfonate available from Ethyl Corporation, Richmond, Virginia, is also suitable for use in the present invention.
  • In a preferred embodiment, the detergent is prepared as an overbased detergent. That is to say, in preparation, the detergent is reacted with a large amount of an inorganic base, e.g. calcium carbonate or magnesium carbonate, and is thus capable of absorbing a large excess of acidic products. One such suitable overbased calcium phenate which is suitable for the practice of the present invention is OLOA 219 C, with a total base number of about 260 also available from Oronite.
  • In another preferred embodiment, sulfonate detergents are used in the levels specified above. One such suitable sulfonate is HiTEC® 611, an overbased calcium detergent with a TBN of about 300, also available from Ethyl Corporation.
  • Finally, also suitable in the present invention are the so-called "superbased" detergents, with exceptionally high TBN (total base number). One such superbased detergent is HiTEC® 607, a 410 TBN calcium sulfonate, also available from Ethyl Corporation.
  • It is preferred to have a mixture of detergents, such as a mixture of overbased calcium phenate and overbased calcium sulfonate, in roughly equal proportions.
  • Component (B) Dispersant
  • Component (B) comprises at least one oil-soluble phosphorus or boron-containing ashless dispersant. The phosphorus or boron-containing ashless dispersants can be formed by phosphorylating or boronating an ashless dispersant having basic nitrogen and/or at least one hydroxyl group in the molecule, such as a succinimide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, hydrocarbyl polyamine dispersant, or polymeric polyamine dispersant.
  • The polyamine succinimides in which the succinic group contains a hydrocarbyl substituent containing at least 30 carbon atoms are described for example in U.S. Pat. Nos. 3,172,892; 3,202,678; 3,216,936; 3,219,666; 3,254,025; 3,272,746; and 4,234,435. The alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group. The alkenyl succinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to, for example, about 180-220 degrees C. The olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1-butene, isobutene and the like and mixtures thereof. The more preferred source of alkenyl group is from polyisobutene having a gel permeation chromotography (GPC) number average molecular weight of up to 10,000 or higher, preferably in the range of about 500 to about 2,500, and most preferably in the range of about 800 to about 1,500.
  • As used herein the term "succinimide" is meant to encompass the completed reaction product from reaction between one or more polyamine reactants and a hydrocarbon-substituted succinic acid or anhydride (or like succinic acylating agent), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
  • Alkenyl succinic acid esters and diesters of polyhydric alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups can be used in forming the phosphorus-containing ashless dispersants. Representative examples are described in U.S. Pat. Nos. 3,331,776; 3,381,022; and 3,522,179. The alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succinimides described above.
  • Suitable alkenyl succinic ester-amides for forming the phosphorylated ashless dispersant are described for example in U.S. Pat. Nos. 3,184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540.
  • Hydrocarbyl polyamine dispersants that can be phosphorylated are generally produced by reacting an aliphatic or alicyclic halide (or mixture thereof) containing an average of at least about 40 carbon atoms with one or more amines, preferably polyalkylene polyamines. Examples of such hydrocarbyl polyamine dispersants are described in U.S. Pat. Nos. 3,275,554; 3,394,576; 3,438,757; 3,454,555; 3,565,804; 3,671,511; and 3,821,302.
  • In general, the hydrocarbyl-substituted polyamines are high molecular weight hydrocarbyl-N-substituted polyamines containing basic nitrogen in the molecule. The hydrocarbyl group typically has a number average molecular weight in the range of about 750-10,000 as determined by GPC, more usually in the range of about 1,000-5,000, and is derived from a suitable polyolefin. Preferred hydrocarbyl-substituted amines or polyamines are prepared from polyisobutenyl chlorides and polyamines having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
  • Mannich polyamine dispersants which can be utilized in forming the phosphorylated ashless dispersant is a reaction product of an alkyl phenol, typically having a long chain alkyl substituent on the ring, with one or more aliphatic aldehydes containing from 1 to about 7 carbon atoms (especially formaldehyde and derivatives thereof), and polyamines (especially polyalkylene polyamines). Examples of Mannich condensation products, and methods for their production are described in U.S. Pat. Nos. 2,459,112; 2,962,442; 2,984,550; 3,036,003; 3,166,516; 3,236,770; 3,368,972; 3,413,347; 3,442,808; 3,448,047; 3,454,497; 3,459,661; 3,493,520; 3,539,633; 3,558,743; 3,586,629; 3,591,598; 3,600,372; 3,634,515; 3,649,229; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,872,019; 3,904,595; 3,957,746; 3,980,569; 3,985,802; 4,006,089; 4,011,380; 4,025,451; 4,058,468; 4,083,699; 4,090,854; 4,354,950; and 4,485,023.
  • The preferred hydrocarbon sources for preparation of the Mannich polyamine dispersants are those derived from substantially saturated petroleum fractions and olefin polymers, preferably polymers of mono-olefins having from 2 to about 6 carbon atoms. The hydrocarbon source generally contains at least about 40 and preferably at least about 50 carbon atoms to provide substantial oil solubility to the dispersant. The olefin polymers having a GPC number average molecular weight between about 600 and 5,000 are preferred for reasons of easy reactivity and low cost. However, polymers of higher molecular weight can also be used. Especially suitable hydrocarbon sources are isobutylene polymers.
  • The preferred Mannich base dispersants for this use are Mannich base ashless dispersants formed by condensing about one molar proportion of long chain hydrocarbon-substituted phenol with from about 1 to 2.5 moles of formaldehyde and from about 0.5 to 2 moles of polyalkylene polyamine.
  • Polymeric polyamine dispersants suitable for preparing phosphorylated ashless dispersants are polymers containing basic amine groups and oil solubilizing groups (for example, pendant alkyl groups having at least about 8 carbon atoms). Such materials are illustrated by interpolymers formed from various monomers such as decyl methacrylate, vinyl decyl ether or relatively high molecular weight olefins, with aminoalkyl acrylates and aminoalkyl acrylamides. Examples of polymeric polyamine dispersants are set forth in U.S. Pat. Nos. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
  • The various types of ashless dispersants described above can be phosphorylated by procedures described in U.S. Pat. Nos. 3,184,411; 3,342,735; 3,403,102; 3,502,607; 3,511,780; 3,513,093; 3,513,093; 4,615,826; 4,648,980; 4,857,214 and 5,198,133.
  • In another preferred embodiment, the dispersants or the phosphorus-containing dispersants of the present invention are also boronated.
  • Methods that can be used for boronating (borating) the various types of ashless dispersants described above are described in U.S. Pat. Nos. 3,087,936; 3,254,025; 3,281,428; 3,282,955; 2,284,409; 2,284,410; 3,338,832; 3,344,069; 3,533,945; 3,658,836; 3,703,536; 3,718,663; 4,455,243; and 4,652,387.
  • Preferred procedures for phosphorylating and boronating ashless dispersants such as those referred to above are set forth in U.S. Pat. Nos. 4,857,214 and 5,198,133.
  • The amount of phosphorylated ashless dispersant on an "active ingredient basis" (i.e., excluding the weight of impurities, diluents and solvents typically associated therewith) is generally within the range of about 0.5 to about 7.5 weight percent (wt%), typically within the range of about 0.5 to 6.5 wt%, preferably within the range of about 0.5 to about 5.5 wt%, and most preferably within the range of about 1.0 to about 4.5 wt%.
  • In a preferred embodiment of the present invention, an ashless dispersant with an N/P ratio as set forth in US Patent 5,972,851, which is incorporated herein by reference. In this preferred embodiment, an optional component of the present invention is a dispersant having a nitrogen to phosphorus mass ratio between about 3:1 and about 10:1. The dispersant of the preferred embodiment can be prepared in at least two ways. In one method, an ashless dispersant is phosphorylated to such a degree that the nitrogen to phosphorus mass ratio between about 3:1 and about 10:1. In another embodiment, a phosphorylated dispersant and a non-phosphorylated dispersant are blended together such that the total nitrogen to phosphorus mass ratio of the dispersant is between about 3:1 and about 10:1.
  • Overall, the dispersant is preferably present in the final fluid in an amount of about 1.00% to about 10.00% by weight, more preferably from about 1.00 weight % to about 7.00 weight %, most preferably about 3-6 weight %.
  • Component (C) Friction Modifier
  • The compositions of the present invention contain at least one amine-based friction modifier, and most preferably a mixture of amine-based friction modifiers. These may be in combination with other friction modifiers as well.
  • The amine-based friction modifiers typically include such compounds as fatty amines or ethoxylated fatty amines, ethoxylated aliphatic ether amines, and fatty tertiary amines. Other suitable nitrogen containing friction modifiers include fatty imidazolines, aliphatic fatty acid amides, and the like. Various other known compounds which are suitable as friction modifiers include aliphatic carboxylic acids, glycerol esters, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, and aliphatic thiophosphates. The aliphatic group may contain above about eight carbon atoms so as to render the compound suitably oil soluble.
  • Suitable friction modifiers also include metal salts of fatty acids. Preferred cations are zinc, magnesium, calcium, barium, and sodium and any alkaline, or alkaline earth metals may, be used. The salts may be overbased by including and excess of cations per equivalent of amine. The excess cations are then treated with carbon dioxide to form the carbonate. The metal salts are prepared by reacting a suitable salt with the acid to form the salt, and where appropriate adding carbon dioxide to the reaction mixture to form the carbonate of any cation beyond that needed to form the salt. A preferred friction modifier is zinc oleate.
  • Also suitable are aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia or other primary amines.
  • One preferred group of friction modifiers is comprised of the N-aliphatic hydrocarbyl-substituted diethanol amines in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms.
  • Some commercially available friction modifiers which are suitable in the practice of the invention are the Armeen® series of primary amines (12D,16D, 18D, O, OD, OL, OLD, C, CD, S, SD, T, TD, HT, and HTD); secondary amines (2C, 2T, 2HT, 2-18); tertiary monoalkyl amines (DM12D, DM16D, DM18D, DMOD, DMCD, DMSD, DMTD, DMHTD); tertiary dialkyl amines (M2C, M2HT); tertiary trialkyl amines (3-12, 3-16); diamines, under the tradename Duomeen® (C, CD, T, TTM, OL, LT-4, S); triamines, under the tradename Triameen® T; tetramines, under the tradename Tetrameen® T; ethoxylated amines, under the tradename Ethomeen® (C-12, C-15, C-20, C-25, O-12, O-15, T-12, T-15, T-25, S-12, S-15, S-20, S-25,18-12,18-20,18-25,18-60); and ethoxylated diamines, under the tradename Ethoduomeen® (T-13, T-20, T-25). Especially preferred are Ethomeen® T-12, an ethoxylated tallow diamine, and Ethomeen® C-12, an ethoxylated cocoalkylamine. All from the above list are available from Akzo Nobel Chemical Company.
  • Also suitable for use as friction modifiers in the scope of the present invention are alkanolamides derived from C12-C18 fatty acids, e.g. cocoamide and tallowamide. Commercial examples of these alkanolamides include Schercomid SL-ML (lauramide diethanolamine), and Schercomid SOA-E, a C18-amide, each available from Scher Chemicals, Inc, New Jersey. Schercomid SL-ML is especially preferred.
  • A particularly preferred friction modifier system is composed of a combination of at least one N-aliphatic hydrocarbyl-substituted diethanolamine and at least one N-aliphatic hydrocarbyl-substituted trimethylene diamine in which the N-aliphatic hydrocarbyl-substituent is at least one straight chain aliphatic hydrocarbyl group free of acetylenic unsaturation and having in the range of about 14 to about 20 carbon atoms. Further details concerning this friction modifier system are set forth in U.S. Pat. Nos. 5,372,735 and 5,441,656, incorporated herein by reference.
  • Another particularly preferred friction modifier system is based on the combination of (i) at least one di(hydroxyalkyl) aliphatic tertiary amine in which the hydroxyalkyl groups, being the same or different, each contain from 2 to about 4 carbon atoms, and in which the aliphatic group is an acyclic hydrocarbyl group containing from about 10 to about 25 carbon atoms, and (ii) at least one hydroxyalkyl aliphatic imidazoline in which the hydroxyalkyl group contains from 2 to about 4 carbon atoms, and in which the aliphatic group is an acyclic hydrocarbyl group containing from about 10 to about 25 carbon atoms. Further details concerning this friction modifier system are set forth in U.S. Pat. No. 5,344,579, incorporated herein by reference.
  • Component (i), the di(hydroxyalkyl) aliphatic tertiary amine, has a nitrogen atom to which are bonded two hydroxyalkyl groups and one non-cyclic aliphatic hydrocarbyl group having 10 to 25 carbon atoms, and preferably 13 to 19 carbon atoms. The hydroxyalkyl groups of these tertiary amines can be the same or different, but each contains from 2 to 4 carbon atoms. The hydroxyl groups can be in any position in the hydroxyalkyl groups, but preferably are in the β-position. Preferably the two hydroxyalkyl groups in component (i) are the same, and most preferably are 2-hydroxyethyl groups. The aliphatic group of these tertiary amines can be straight or branched chain and it can be saturated or olefinically unsaturated and if unsaturated, it typically contains from one to three olefinic double bonds. Component (i) can have a single type of aliphatic group or it can comprise a mixture of compounds having different aliphatic groups in which the average number of carbon atoms falls within the foregoing range of from 10 to 25 carbon atoms.
  • Another set of friction modifiers which is suitable for practice within the scope of the present invention includes: 1) at least one dihydroxy alkyl aliphatic tertiary amine (e.g., alkyl C12-C18 and cyclic hydrocarbyl); and 2) at least one aliphatic fatty alkanol amide in which the aliphatic group is an acyclic hydrocarbyl group containing from 12 to 18 carbon atoms. The aliphatic fatty alkanol is preferably a dihydroxy alkyl. Especially preferred is an aliphatic primary amine, an aliphatic secondary amine, or a mixture thereof, in which the aliphatic group contains from 12 to 18 carbon atoms.
  • From the foregoing it will be clear that component (i) can be a single compound or a mixture of compounds meeting the structural criteria described above.
  • The hydroxyalkyl aliphatic imidazolines, component (ii), suitable for use in the practice of this invention are characterized by having in the 1-position on the imidazoline ring a hydroxyalkyl group that contains from 2 to 4 carbon atoms, and by having in the adjacent 2-position on the ring a non-cyclic hydrocarbyl group containing 10 to 25 carbon atoms. While the hydroxyl group of the hydroxyalkyl group can be in any position thereof, it preferably is on the β-carbon atom, such as 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl. Typically the aliphatic group is a saturated or olefinically unsaturated hydrocarbyl group, and when olefinically unsaturated, the aliphatic group may contain one, two or three such double bonds. Component (ii) may be a single substantially pure compound or it may be a mixture of compounds in which the aliphatic group has an average of from 10 to 25 carbon atoms. Preferably the aliphatic group has 15 to 19 carbon atoms, or an average of 15 to 19 carbon atoms. Most preferably the aliphatic group has, or averages, 17 carbon atoms. The aliphatic group(s) may be straight or branched chain groups, with substantially straight chain groups being preferred. A particularly preferred compound is 1-hydroxyethyl-2-heptadecenyl imidazoline. A commercially available imidazoline based friction modifier essentially suitable for use as ii) in the invention is Unamine O, available from Lonza Chemicals.
  • It will thus be clear that component (ii) can be a single compound or a mixture of compounds meeting the structural criteria described above.
  • Generally speaking, the fully formulated final compositions of this invention will optionally contain up to about 1.25 wt% on an active ingredient basis, and preferably from about 0.005 to about 1.10 wt% on an active ingredient basis of one or more friction modifiers, most preferably about 0.005 to about 1.00 wt %.
  • In addition to the above mandatory components, the following optional components may also be present in compositions according to the present invention.
  • Component (D) Antioxidants
  • The compositions of the present invention may include one or more antioxidants, for example, one or more phenolic antioxidants, hindered phenolic antioxidants, additional sulfurized olefins, aromatic amine antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants (e.g. organic phosphites), and mixtures thereof.
  • Suitable exemplary compounds include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), mixed methylene-bridged polyalkyl phenols, 4,4'-thiobis(2-methyl-6-tert-butylphenol), N,N'-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenyl amine, phenyl- α-naphthyl amine, and phenyl-β-naphthyl amine.
  • Especially preferred antioxidants include diphenyl amine derived antioxidants; such as Naugalube® 438-L.
  • In the class of amine antioxidants, oil-soluble aromatic secondary amines; aromatic secondary monoamines; and others are suitable. Suitable aromatic secondary monoamines include diphenylamine, alkyl diphenylamines containing 1 to 2 alkyl substituents each having up to about 16 carbon atoms, phenyl-α-naphthylamine, phenyl- γ-naphthylamine, alkyl- or aralkylsubstituted phenyl- α-naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkyl- or aralkyl-substituted phenyl- β-naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkylated p-phenylene diamines available from Goodyear under the tradename "Wingstay 100" and from Uniroyal, and similar compounds.
  • The preferred type of aromatic amine antioxidant is that embodied in the commercial product Naugalube 483L is an alkylated diphenylamine of the general formula : R1--C6H4--NH--C6H4--R2 wherein R1 is an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms) and R2 is a hydrogen atom or an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms). Most preferably, R1 and R2 are the same. Particularly preferred is a nonylated diphenyl amine containing 4,4'-dinonylated diphenyl amine; a bis(4-nonylphenyl)(amine) wherein the nonyl groups are branched.
  • In the class of phenolic antioxidants, suitable compounds include ortho-alkylated phenolic compounds, e.g. 2-tert-butylphenol, 2,6-di-tertbutylphenol, 4-methyl-2,6-di-tertbutylphenol, 2,4,6-tri-tertbutylphenol, and various analogs and homologs or mixtures thereof; one or more partially sulfurized phenolic compounds as described in US Patent 6,096,695, the disclosure of which is incorporated herein by reference; methylene-bridged alkylphenols as described in U.S. Pat. No. 3,211,652, the disclosure of which is incorporated herein by reference.
  • Antioxidants may be optionally included in the fully formulated final inventive lubricating composition at from about 0.00 to about 5.00 weight percent, more preferably from about 0.01 weight % to about 1.00 weight %, most preferably about 0.05 wt % to about 0.50 wt %.
  • Component (E) Extreme Pressure/Anti-Wear
  • The automatic transmission fluids of the present invention may further include anti-wear/extreme pressure additives.
  • When the desired phosphorus content of the finished fluid is not completely supplied by use of a phosphorus-containing ashless dispersant (or a boron- and phosphorus-containing ashless dispersant), the remainder of the phosphorus content is preferably supplied by inclusion in the composition of one or more phosphorus-containing esters or acid-esters such as oil-soluble organic phosphites, oil-soluble organic acid phosphites, oil-soluble organic phosphates, oil-soluble organic acid phosphates, oil-soluble phosphoramidates. Examples include trihydrocarbyl phosphates, trihydrocarbyl phosphites, dihydrocarbyl phosphates, dihydrocarbyl phosphonates or dihydrocarbyl phosphites or mixtures thereof, monohydrocarbyl phosphates, monohydrocarbyl phosphites, and mixtures of any two or more of the foregoing. Oil-soluble amine salts of organic acid phosphates are a preferred category of auxiliary phosphorus-containing additives for use in the fluids of this invention. Sulfur-containing analogs of any of the foregoing compounds can also be used, but are less preferred. Suitable commercially available auxiliary phosphorus additives include amine phosphate antiwear/extreme pressure agents, available from Ciba-Geigy Corporation as Irgalube® 349 and R.T. Vanderbilt Inc. as Vanlube® 672.
  • Also suitable are sulfurized fatty acid esters, e.g. the Sul-Perm® brand of sulfurized fatty acid esters from Keil Chemical, and sulfurized dithiocarbamates, and alkyl thiadiazoles such as HiTEC® 4312 and 4313, available from Ethyl Corporation, Richmond, Virginia.
  • The extreme pressure/anti wear additive is preferably present in the final fully-formulated fluid in an amount of from 0.00 to about 1.00 weight %, more preferably from about 0.01 to about 0.50 weight %.
  • Component (F) - Viscosity Index Improver
  • The compositions of the present invention optionally, but preferably, contain a viscosity index improver (VII). Preferred VIIs include, but are not limited to, olefin copolymer VIIs, polyalkylmethacrylate VIIs and styrene-maleic ester VIIs. Of these, polyalkylmethacrylate VIIs are particularly preferred. The viscosity index improver is supplied in the form of a solution in an inert solvent, typically a mineral oil solvent, which usually is a severely refined mineral oil. The viscosity index improver solution as received often will have a boiling point above 200°C, and a specific gravity of less than 1 at 25 °C. Preferably, the viscosity index improver will have sufficient shear stability such that the finished composition possesses a kinematic viscosity of at least 5, and more preferably at least 6.8, cSt at 100 °C after 40 cycles in the FISST (Fuel Injector Shear Stability Test) of ASTM D-5275.
  • The VII in the present invention will also preferably have less than 5% shear loss on the tapered roller bearing test.
  • On an active ingredient basis (i.e., excluding the weight of inert diluent or solvent associated with the viscosity index improver as supplied), the finished fluid compositions of this invention will normally contain in the range of about 0 to about 15 wt% of the polymeric viscosity index improver. Small departures from this range may be resorted to as necessary or desirable in any given situation.
  • Suitable materials for use as component (F) include styrene-maleic ester VIIs such as LUBRIZOL® 3702, LUBRIZOL®3706 and LUBRIZOL®3715 available from The Lubrizol Corporation; polyalkylmethacrylate VIIs such as those available from RÖHM GmbH (Darmstadt, Germany) under the trade designations: VISCOPLEX® 5543, VISCOPLEX® 5548, VISCOPLEX® 5549, VISCOPLEX® 5550, VISCOPLEX® 5551 and VISCOPLEX® 5151, from Rohm & Haas Company (Philadelphia, Pennsylvania) under the trade designations ACRYLOID® 1277, ACRYLOID® 1265 and ACRYLOID® 1269, and from Ethyl Corporation (Richmond, Virginia) under the trade designation HiTEC® 5710 viscosity index improver; and olefin copolymer VIIs such as HiTEC® 5747 VII, HiTEC® 5751 VII, HiTEC® 5770 VII and HiTEC® 5772 VII available from Ethyl Corporation and SHELLVIS® 200 available from Shell Chemical Company. Mixtures of the foregoing products can also be used as well as dispersant and dispersant/antioxidant VIIs.
  • Preferably, the viscosity index improver will be provided as a hydrocarbon solution having a polymer content in the range of from about 25 to about 80 wt% and a nitrogen content in the range of about 0 to about 0.5 wt%. Such products preferably exhibit a permanent shear stability index (a PSSI value) using ASTM test method D-3945A of no higher than about 75, preferably 50 or less, and most preferably 35 or less.
  • Preferred is a dispersant polymethacrylate viscosity index improver such as HiTEC® 5738, or a non dispersant polymethacrylate viscosity index improver such as HiTEC®5739, both products of Ethyl Corporation, Richmond Virginia, or a mixture of dispersant and non-dispersant viscosity index improvers. Especially preferred is an ultra high shear stable dispersant polymethacrylate viscosity index improver such as HITEC 5769, also a product of Ethyl Corporation, Richmond, Virginia.
  • Quantitatively, the viscosity index improver may be present in an amount of from 0-25% by weight, preferably from 5-20% by weight.
  • Component (G) - Anti-Rust
  • Various known anti-rust agents or additives are known for use in transmission fluids, and are suitable for use in the fluids according to the present invention. Especially preferred are alkyl polyoxyalkylene ethers, such as Mazawet® 77, C-8 acids such as Neofat® 8, oxyalkyl amines such as Tomah PA-14, 3-decyloxypropylamine, and polyoxypropylene-polyoxyethylene block copolymers such as Pluronic® L-81.
  • Mixtures of the above anti-rust agents are especially preferred. Anti-rust agents are preferably used in low quantities, e.g. less than about 0.2 wt %, preferably from about 0.01 to about 0.15 weight %.
  • Component (H) - Anti-Foam/Surfactant
  • Anti-foam/Surfactant agents may also be included in a fluid according to the present invention. Various agents are known for such use. Especially preferred are copolymers of ethyl acrylate and hexyl ethyl acrylate, such as PC-1244, available from Solutia. Also preferred are silicone fluids such as 4% DCF. Mixtures of anti-foam agents are especially preferred.
  • Given their high activity levels, anti foam agents are generally present in small amounts, from about 0.00 - 0.10 weight %, more preferably between about 0.02-0.07 wt %, most preferably about 0.05 wt %.
  • Component (I) - Dye
  • It is preferred to add a colorant to the fluid to give it a unique character which is detectable. Generally, azo class dyes are used, such as C.I. Solvent Red 24 or C.I. Solvent Red 164, as set forth in the "Colour Index" of the American Association of Textile Chemists and Colorists and the Society of Dyers and Colourists (U.K.) which is incorporated herein by reference. For automatic transmission fluids, Automate Red Dye is especially preferred. Dye is present in a very minimal amount, usually less than 400 ppm, preferably between about 200-300 ppm in the finished oil.
  • Component (J) - Oil
  • If the additives are provided in an additive package concentrate, a suitable carrier diluent is added to ease blending, solubilizing, and transporting the additive package. The diluent oil needs to be compatible with the base oil and the additive package. Generally, the diluent is present in the concentrate in an amount of between 5-20%, although it can vary widely with application. Generally speaking, less diluent is preferable as it lowers transportation costs and treat rates. A suitable diluent is a process oil of lubricating viscosity.
  • If the inventive composition is to be prepared as a concentrate, then base oil may be omitted and an appropriate adjustment made in the weight % of each of the above optional and mandatory ingredients to prepare a suitable concentrate, taking care that solubility and compatibility is maintained. However, if a fully formulated fluid is to be prepared, then base oil is a mandatory component.
  • The base oils used in forming the automatic transmission fluids of this invention can be any suitable natural or synthetic oil having the necessary viscosity properties for this usage. Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil etc.), liquid petroleum oils and hydrorefined, severely hydrotreated, iso-dewaxed, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • The synthetic lubricating oils suitable for use in this invention include one of any number of commonly used synthetic hydrocarbon oils, which include, but are not limited to, poly-alpha-olefins, synthetic esters, alkylated aromatics, alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification etc., esters of dicarboxylic acids and silicon-based oils. Thus, the base oil may be composed entirely of a natural oil such as mineral oil of suitable viscosity or it may be composed entirely of a synthetic oil such as a poly-alpha-olefin oligomer of suitable viscosity.
  • Likewise, the base oil may be a blend of natural and/or synthetic base oils provided that the blend has the requisite properties for use in the formation of an automatic transmission fluid. Ordinarily, the base oil should have a kinematic viscosity in the range of 3 to 8 centistokes (cSt) at 100 °C. Preferred automatic transmission fluids used in the practice of this invention can be formulated without a viscosity index improver so as to possess a kinematic viscosity of at least 3.0 cSt at 100°C and a Brookfield viscosity of no more than 20,000 cP at -40 °C, or formulated using a viscosity index improver so as to possess a kinematic viscosity of at least 6.8 cSt at 100 °C and a Brookfield viscosity of no more than 20,000 cP at -40 °C.
  • Suitable base stock oil includes, preferably, Group I, II, and III base oils, as are known to those of skill in the art. In certain instances, usually depending on the final use of the lubricant composition according to the present invention, Group I is preferred, and in other instances, Group II and III are preferred.
  • Group I base stocks contain less than 90% saturates (as determined by ASTM D 2007) and/or greater than 0.03 percent sulfur (as determined by ASTM D 2622, D 4294, D 4927, or D 3120) and have a viscosity index greater than or equal to 80 and less than 120 (as determined by ASTM D 2270).
  • Group II base stocks contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulfur and have a viscosity index greater than 80 and less than 120 using the above noted test methods. Group II + oils may also be used. These are oils which have a VI at the high end of the VI spectrum, e.g. about 120.
  • Group III base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 % sulfur and have a viscosity index greater than or equal to 120 using the tests noted above.
  • In another embodiment, the transmission fluid contains less than 5% poly-alpha-olefins (PAO) and is more preferably PAO free.
  • Component (K) - Additional Components Seal Swell Agents
  • The automatic transmission fluids of the present invention may further include seal swell agents. Seal swell agents such as esters, adipates, sebacates, azealates, phthalates, sulfones, alcohols, alkylbenzenes, substituted sulfolanes, aromatics, or mineral oils cause swelling of elastomeric materials used as seals in engines and automatic transmissions.
  • Alcohol-type seal swell agents are generally low volatility linear alkyl alcohols, such as decyl alcohol, tridecyl alcohol and tetradecyl alcohol.
  • Alkylbenzenes useful as seal swell agents include dodecylbenzenes, tetradecylbenzenes, dinonyl-benzenes, di(2-ethylhexyl)benzene, and the like.
  • Substituted sulfolanes (e.g. those described in U.S. Pat. No. 4,029,588, incorporated herein by reference) are likewise useful as seal swell agents in compositions according to the present invention.
  • Mineral oils useful as seal swell agents in the present invention include low viscosity mineral oils with high naphthenic or aromatic content.
  • Aromatic seal swell agents include the commercially available Exxon Aromatic 200 ND seal swell agent.
  • Commercially available examples of mineral oil seal swell agents include Exxon® Necton®-37 (FN 1380) and Exxon® Mineral Seal Oil (FN 3200).
  • When used in the ATF of the present invention, a seal swell agent will typically comprise from about 1 to about 30 wt. %, preferably from about 1 to about 20 wt. %, most preferably from about 1 to about 10 wt. %, based on the total weight of ATF.
  • Corrosion Inhibitors
  • The automatic transmission fluids of the present invention may further include additional corrosion inhibitors (it should be noted that some of the earlier mentioned components, e.g. monoalkyl and dialkyl thiadiazole each have copper corrosion inhibition properties). Other suitable additional inhibitors of copper corrosion include ether amines, polyethoxylated compounds such as ethoxylated amines and ethoxylated alcohols, imidazolines, and the like.
  • Thiazoles, triazoles and thiadiazoles may also be used in the present invention. Examples include benzotriazole; tolyltriazole; octyltriazole; decyltriazole; dodecyltriazole; 2-mercaptobenzothiazole; 2,5-dimercapto-1,3,4-thiadiazole; 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles; and 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles. The preferred compounds are the 1,3,4-thiadiazoles, especially the 2-hydrocarbyldithio-5-mercapto-1,3,4-dithiadiazoles, a number of which are available as articles of commerce. These may be present in an amount of from 0.00 to 0.50 weight percent, more preferably from about 0.01 to about 0.10 weight percent, based on the final formulation.
  • In selecting any of the foregoing optional additives, it is important to ensure that the selected component(s) is/are soluble or stably dispersible in the additive package and finished ATF composition, are compatible with the other components of the composition, and do not interfere significantly with the performance properties of the composition, such as the friction, viscosity and/or shear stability properties, needed or at least desired in the overall finished composition.
  • In general, the ancillary additive components are employed in the oils in minor amounts sufficient to improve the performance characteristics and properties of the base fluid. The amounts will thus vary in accordance with such factors as the viscosity characteristics of the base fluid employed, the viscosity characteristics desired in the finished fluid, the service conditions for which the finished fluid is intended, and the performance characteristics desired in the finished fluid. However, generally speaking, the following concentrations (weight percent unless indicated otherwise) of the additional components (active ingredients) in the base fluids are illustrative:
    Component Typical Range Preferred Range
    D 0.00 - 5.00 wt % 0.01-1.00 wt %
    E 0.00 - 1.00 wt % 0.01 - 0.50 wt %
    F 0 - 25 wt % 2-20 wt %
    G 0.00 - 0.2 wt % 0.01 - 0.15 wt %
    H 0.00 - 0.10 wt % 0.20 - 0.70 wt %
    I < 400 ppm 200-300 ppm
    J Balance Balance
  • It will be appreciated that the individual components employed can be separately blended into the base fluid or can be blended therein in various subcombinations, if desired. Ordinarily, the particular sequence of such blending steps is not critical. Moreover, such components can be blended in the form of separate solutions in a diluent. It is preferable, however, to blend the additive components used in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
  • Additive concentrates can thus be formulated to contain all of the additive components and if desired, some of the base oil component, in amounts proportioned to yield finished fluid blends consistent with the concentrations described above. In most cases, the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate. Thus concentrates containing up to about 50% by weight of one or more diluents or solvents can be used, provided the solvents are not present in amounts that interfere with the low and high temperature and flash point characteristics and the performance of the finished power transmission fluid composition. In this connection, the additive components utilized pursuant to this invention should be selected and proportioned such that an additive concentrate or package formulated from such components will have a flash point of 170 °C or above, and preferably a flash point of at least 180 °C, using the ASTM D-92 test procedure.
  • In the present invention, the finished fluid or concentrate should be essentially free of phenolic antioxidants and sulfurized fats.
  • EXAMPLES
  • Illustrative compositions suitable for use in the practice of this invention are presented in the following Examples, wherein all parts and percentages are by weight unless specified otherwise.
  • The fluids prepared in the Examples were then subjected to testing under commonly known tests, including the low speed SAE #2 rig, under the conditions noted, and the GM plate clutch friction test (GM performance specification GM 6417 M, April 1997) run according to Dexron® III procedures. Briefly, this test involves engaging the clutch at the rate of four cycles per minute for 100 hours (i.e., 24,000 cycles) at 135 degrees C. The DEXRON® III Band Clutch Test limit for the mid-point torque is 185-220 Nm.
  • The GM Dexron III Cycling Test (GM-6297-M), revised April 1993; corresponding to the Ford Mercon V Friction Durability Test (Dexron 5 Specification 3.9, Revised Jul 1, 1996 and October 1, 1998 which sets limits on shift times for 20,000 shift cycles. Shifting from 1st to 2nd gear, 0.30-0.75 seconds; from 2nd to 3rd gear 0.30 to 0.75 sec.
  • The FZG wear test, conducted in the FZG gear rig test machine. This test, IP (Institute of Petroleum) 334/79, which is incorporated herein by reference, measures lubricity, and in the test, two steel spin gears are rotated together for a series of 75 minute stages. The relative torque between the gears is increased by a fixed amount after each stage and the gears are run together for a given period after which they are examined for wear or damage. The result of the test is quoted in terms of the final pass stage and the first fail stage. The test is technically equal to ASTM D 5182-97. This test can be conducted at selected temperatures, nominally 90 degrees C and 150 degrees C.
  • Finally, the compositions were subjected to the Aluminum Beaker Oxidation Test (ABOT) as described in SAE Technical paper series 881673. Compositions according to the present invention resisted oxidation for at least 500 hours.
  • All publications, patents, or other generally known information cited above is incorporated herein by reference as if fully set forth herein.
    Composition of Examples
    Component Composition Ex. 3 (invention) Ex. 2 (not of invention) Ex. 3. (commercially avail. Product)
    A Overbase Calcium Sulfonate Detergent 0.5 0.00 Believed to have 500-600 ppm deterg.
    Overbase Calcium Phenate Detergent 0.5 0.05
    B Boronated phosphorylated succinimide dispersant 3.77 3.77 Believed to have a conventional additive pack, which would include VII, a friction modifier, antioxidants, anti foam agents and other conventional optional components.
    C Ethoxylated Amine; n-alkyl tallow amine 0.08 0.15
    C n-oleyl diamino propane 0.003 0.005
    D Diphenyl amine 0.26 0.20
    D Phenolic antioxidant (2,6-di tert-butyl phenol) 0.20 0.00
    E, F, G, H, I , J EP agents, VII, anti-rust; anti foam; dyes, and base oils 94.677 95.135
    TOTAL 100.00 100.00 100.00
  • Turning now to Figures 1-6, it may clearly be seen that, when compared to comparative examples 1 and 2, a composition according to the present invention has excellent initial anti-shudder properties, excellent friction durability, extended anti-shudder performance, and oxidation resistance.
  • With specific reference to Figure 1, it may be seen that the coefficient of friction for fluids of example 3 (according to the invention) remains within the acceptable parameters of the ECCC Friction durability test on the SAE #2 rig of 200 hours under the stated conditions. The coefficient of friction, even after 216 hours, remains between 0.140 and 0.150.
  • Turning now to figure 2, it may be seen that the friction durability of fluids according to example 3, when calculated on hours to negative slope (which indicates presence of shudder) lasts at least 200 hours.
  • Turning now to figure 3, the GM plate clutch friction test (anti-shudder) under the stated conditions, it is clear that after 3600 cycles, the fluid according to the present invention has a level tail without the characteristic rooster tail which indicates shudder or stick-slip as seen in Examples 1 and 2.
  • The presence of a significant "rooster tail" in this test would indicate a problem with poor or rough shift feel characteristics in the vehicle which used the fluid.
  • Turning now to figure 4, it may be seen that the initial anti-shudder characteristics of the instant inventive fluid compositions are at least as good as any of the comparative examples in the GM plate clutch friction test under the stated conditions.
  • Figure 5 illustrated the degradation in performance of a fluid of comparative example 2 (not of the invention) under the ECCC friction durability test run on the SAE #2 low speed rig. After about 72 hours, a considerable degradation is seen. Thereafter, the vehicle can be expected to shudder.
  • Figure 6 illustrates the ECCC friction durability results on the SAE #2 low speed rig for Example 2. The coefficient of friction has dropped, after 120 hours, to between 0.130 and 0.120, which would result in the loss of torque and fuel economy in a vehicle.
  • This invention is susceptible to considerable variation in its practice. Accordingly, this invention is not limited to the specific exemplifications set forth hereinabove. Rather, this invention is within the spirit and scope of the appended claims, including the equivalents thereof available as a matter of law.
  • The patentee does not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part of the invention under the doctrine of equivalents.

Claims (19)

  1. An automatic transmission fluid, comprising:
    (1) a major amount of a base oil, and
    (2) a minor amount of an additive comprising:
    (A) at least 0.10 wt. %, based on the fluid, of a metal-containing detergent,
    (B) a dispersant, and
    (C) a mixture of at least two different friction modifiers.
  2. An automatic transmission fluid, comprising:
    (1) a major amount of a base oil and
    (2) a minor amount of an additive comprising:
    (A) at least 0.25 wt %, based on the fluid, of a metal-containing detergent,
    (B) a dispersant, and
    (C) a mixture of at least two amine-based friction modifiers.
  3. An automatic transmission fluid as claimed in Claim 1 or Claim 2, wherein component (A) is a calcium containing detergent.
  4. An automatic transmission fluid as claimed in Claim 3, wherein component (A) is a calcium phenate, calcium sulfonate, or mixture thereof.
  5. An automatic transmission fluid as claimed in any preceding claim, wherein the metal containing detergent is an overbased calcium sulfonate.
  6. An automatic transmission fluid as claimed in any preceding claim, wherein component (A) is present in an amount from 0.25 to 1.5 wt. %.
  7. An automatic transmission fluid as claimed in Claim 6, wherein component (A) is present in an amount from 0.75 wt. % to 1.00 wt. %.
  8. An automatic transmission fluid as claimed in any preceding claim, wherein component (B) is a succinimide dispersant.
  9. An automatic transmission fluid as claimed in Claim 8, wherein the succinimide is boronated, phosphorylated, or boronated and phosphorylated.
  10. An automatic transmission fluid as claimed in any preceding claim, wherein the mixture of friction modifiers comprises a mixture of an ethoxylated amine and a fatty polyamine.
  11. An automatic transmission fluid as claimed in any preceding claim, wherein component C is selected from the group consisting of ethoxylated fatty amines, aliphatic fatty alkanol amides, aliphatic primary amines, aliphatic secondary amines, and aliphatic fatty imidazolines.
  12. An automatic transmission fluid as claimed in any preceding claim further comprising at least one viscosity index improver, antioxidant, anti rust, or anti foam agent.
  13. An automatic transmission fluid as claimed in any preceding claim, further comprising an additional phosphorus source.
  14. An automatic transmission fluid as claimed in Claim 13, wherein the phosphorus source is dibutyl hydrogen phosphite.
  15. An automatic transmission fluid as claimed in any preceding claim, further comprising a shear stable viscosity index improver.
  16. The automatic transmission fluid as claimed in any preceding claim further comprising at least one additive selected from the group consisting of extreme pressure/antiwear agents, seal swell agents, foam inhibitors, rust inhibitors, viscosity index improvers, lubricity agents, and dyes.
  17. The automatic transmission fluid as claimed in any preceding claim, wherein the fluid has a friction durability of at least 200 hours on the ECCC friction durability test as measured on the SAE #2 low speed rig.
  18. A method of improving friction durability and anti-shudder performance of an automatic transmission said method comprising adding to said automatic transmission an automatic transmission fluid according to any preceding claim; and operating said automatic transmission.
  19. Use in a transmission fluid comprising:
    (1) a major amount of a base oil; and
    (2) a minor amount of an additive comprising:
    (A) at least 0.10 %, based on the fluid, of a metal-containing detergent,
    (B) a dispersant, and
    (C) a mixture of at least two different friction modifiers
    to improve the friction durability and anti-shudder performance of the transmission.
EP02250876A 2001-02-14 2002-02-08 Automatic transmission fluids with improved anti-shudder properties Withdrawn EP1233054A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US783065 2001-02-14
US09/783,065 US20020151441A1 (en) 2001-02-14 2001-02-14 Automatic transmission fluids with improved anti-shudder properties

Publications (1)

Publication Number Publication Date
EP1233054A1 true EP1233054A1 (en) 2002-08-21

Family

ID=25128056

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02250876A Withdrawn EP1233054A1 (en) 2001-02-14 2002-02-08 Automatic transmission fluids with improved anti-shudder properties

Country Status (3)

Country Link
US (1) US20020151441A1 (en)
EP (1) EP1233054A1 (en)
JP (1) JP2002275492A (en)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1508611A2 (en) * 2003-08-22 2005-02-23 Nissan Motor Company, Limited Low-friction sliding member in transmission, and transmission oil therefor
EP1518921A1 (en) * 2003-09-23 2005-03-30 Afton Chemical Corporation Power transmission fluids having extended friction durability
EP1529831A2 (en) * 2003-11-10 2005-05-11 Afton Chemical Corporation Lubricant compositions for power transmitting fluids
EP1541665A1 (en) * 2003-12-09 2005-06-15 Infineum International Limited Power transmission fluids with improved friction characteristics
EP1568759A2 (en) 2004-02-27 2005-08-31 Afton Chemical Corporation Power transmission fluids
EP1645616A1 (en) * 2004-10-08 2006-04-12 Afton Chemical Corporation Power transmission fluids with enhanced antishudder durability
WO2006045044A1 (en) * 2004-10-19 2006-04-27 The Lubrizol Corporation Secondary and tertiary amines as friction modifiers for automatic transmission fluids
EP1739159A2 (en) * 2005-06-30 2007-01-03 Afton Chemical Corporation Methods for improved power transmission performance and lubricating compositions therefor
EP1739321A3 (en) * 2005-06-30 2007-01-10 Afton Chemical Corporation Methods for improved power transmission performance
US7273655B2 (en) 1999-04-09 2007-09-25 Shojiro Miyake Slidably movable member and method of producing same
WO2007121205A2 (en) * 2006-04-12 2007-10-25 The Lubrizol Corporation Hydroxy-containing tertiary amines as friction modifiers for automatic transmission fluids
GB2439172A (en) * 2006-06-16 2007-12-19 Afton Chemical Corp Power transmission fluid with enhanced friction characteristics
EP1739158A3 (en) * 2005-06-30 2009-12-16 Afton Chemical Corporation Methods for improved power transmission performance and lubricating compositions therefor
US7771821B2 (en) 2003-08-21 2010-08-10 Nissan Motor Co., Ltd. Low-friction sliding member and low-friction sliding mechanism using same
US8096205B2 (en) 2003-07-31 2012-01-17 Nissan Motor Co., Ltd. Gear
US8152377B2 (en) 2002-11-06 2012-04-10 Nissan Motor Co., Ltd. Low-friction sliding mechanism
US8206035B2 (en) 2003-08-06 2012-06-26 Nissan Motor Co., Ltd. Low-friction sliding mechanism, low-friction agent composition and method of friction reduction
US8575076B2 (en) 2003-08-08 2013-11-05 Nissan Motor Co., Ltd. Sliding member and production process thereof
CN105524679A (en) * 2014-09-28 2016-04-27 中国石油化工股份有限公司 Automatic transmission liquid composition and method for improving dynamic friction coefficient of automatic transmission liquid composition
EP3067408A1 (en) * 2015-03-12 2016-09-14 Afton Chemical Corporation Lubricant composition for automatic transmissions
US9469825B2 (en) 2015-03-12 2016-10-18 Afton Chemical Corporation Lubricant composition for automatic transmissions
WO2019073008A1 (en) * 2017-10-11 2019-04-18 Volkswagen Ag Lubricant composition, use for lubricating a transmission system and transmission system
US11578287B1 (en) 2021-12-21 2023-02-14 Afton Chemical Corporation Mixed fleet capable lubricating compositions
US11807827B2 (en) 2022-01-18 2023-11-07 Afton Chemical Corporation Lubricating compositions for reduced high temperature deposits
US11912955B1 (en) 2022-10-28 2024-02-27 Afton Chemical Corporation Lubricating compositions for reduced low temperature valve train wear
US11926804B1 (en) 2023-01-31 2024-03-12 Afton Chemical Corporation Dispersant and detergent systems for improved motor oil performance
US11970671B2 (en) 2022-07-15 2024-04-30 Afton Chemical Corporation Detergent systems for oxidation resistance in lubricants

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7737092B2 (en) * 2002-05-09 2010-06-15 The Lubrizol Corporation Continuously variable transmission fluids comprising a combination of calcium-and magnesium-overbased detergents
US6884855B2 (en) * 2003-01-30 2005-04-26 Chevron Oronite Company Llc Sulfurized polyisobutylene based wear and oxidation inhibitors
US20050014656A1 (en) * 2003-07-16 2005-01-20 The Lubrizol Corporation Transmission lubricating compositions with improved performance, containing acid/polyamine condensation product
US20050124508A1 (en) * 2003-12-04 2005-06-09 Iyer Ramnath N. Compositions for improved friction durability in power transmission fluids
US20050192186A1 (en) * 2004-02-27 2005-09-01 Iyer Ramnath N. Lubricant compositions for providing anti-shudder performance and elastomeric component compatibility
US20050277560A1 (en) * 2004-06-09 2005-12-15 The Lubrizol Corporation Hydrocarbon compositions to reduce scuffing and seizure of the metal on metal interface for continuously variable transmissions
US20060135375A1 (en) * 2004-12-21 2006-06-22 Chevron Oronite Company Llc Anti-shudder additive composition and lubricating oil composition containing the same
US7485734B2 (en) * 2005-01-28 2009-02-03 Afton Chemical Corporation Seal swell agent and process therefor
JP4677359B2 (en) * 2005-03-23 2011-04-27 アフトン・ケミカル・コーポレーション Lubricating composition
US7482312B2 (en) * 2005-04-01 2009-01-27 Shell Oil Company Engine oils for racing applications and method of making same
CA2633095A1 (en) * 2005-12-15 2007-10-04 The Lubrizol Corporation Lubricant composition for a final drive axle
US20090247438A1 (en) * 2008-03-31 2009-10-01 Exxonmobil Research And Engineering Company Hydraulic oil formulation and method to improve seal swell
CA2912063A1 (en) 2013-05-14 2014-11-20 The Lubrizol Corporation Lubricating composition and method of lubricating a transmission
FR3014898B1 (en) * 2013-12-17 2016-01-29 Total Marketing Services LUBRICATING COMPOSITION BASED ON FATTY TRIAMINES
JP6533689B2 (en) * 2015-04-22 2019-06-19 出光興産株式会社 Automatic transmission oil
US10421922B2 (en) 2015-07-16 2019-09-24 Afton Chemical Corporation Lubricants with magnesium and their use for improving low speed pre-ignition
US10336959B2 (en) 2015-07-16 2019-07-02 Afton Chemical Corporation Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition
US10550349B2 (en) 2015-07-16 2020-02-04 Afton Chemical Corporation Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition
US10377963B2 (en) 2016-02-25 2019-08-13 Afton Chemical Corporation Lubricants for use in boosted engines
US11155764B2 (en) 2016-05-05 2021-10-26 Afton Chemical Corporation Lubricants for use in boosted engines
US10443011B2 (en) 2017-01-18 2019-10-15 Afton Chemical Corporation Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition
US10370615B2 (en) * 2017-01-18 2019-08-06 Afton Chemical Corporation Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition
US10443558B2 (en) 2017-01-18 2019-10-15 Afton Chemical Corporation Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance
US11479735B2 (en) * 2021-03-19 2022-10-25 Afton Chemical GmbH Lubricating and cooling fluid for an electric motor system
US11939551B1 (en) 2023-06-27 2024-03-26 Afton Chemical Corporation Lubricating fluid for an electric motor system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4909952A (en) * 1989-01-03 1990-03-20 The Lubrizol Corporation Sulfur-containing polymeric polyesters and additive concentrates and lubricating oils containing same
WO1993021289A1 (en) * 1992-04-15 1993-10-28 Exxon Chemical Patents Inc. Lubricant composition containing mixed friction modifiers
US5372735A (en) * 1994-02-10 1994-12-13 Ethyl Petroleum Additives, Inc. Automatic transmission fluids and additives therefor
EP0747464A1 (en) * 1995-06-09 1996-12-11 The Lubrizol Corporation A composition for providing anti-shudder friction durability performance for automatic transmissions
US5851962A (en) * 1992-08-18 1998-12-22 Ethyl Japan Corporation Lubricant composition for wet clutch or wet brake
WO2000073406A1 (en) * 1999-05-28 2000-12-07 Infineum International Limited Zinc-free continuously variable transmission fluid

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441656A (en) * 1994-02-10 1995-08-15 Ethyl Petroleum Additives, Inc. Automatic transmission fluids and additives therefor
US5750476A (en) * 1995-10-18 1998-05-12 Exxon Chemical Patents Inc. Power transmitting fluids with improved anti-shudder durability
JPH09263782A (en) * 1996-03-28 1997-10-07 Idemitsu Kosan Co Ltd Oil composition for non-stage transmission
US5972851A (en) * 1997-11-26 1999-10-26 Ethyl Corporation Automatic transmission fluids having enhanced performance capabilities
JP3026195B2 (en) * 1998-08-17 2000-03-27 本田技研工業株式会社 Lubricating oil composition for automatic transmission
JP3977941B2 (en) * 1998-10-07 2007-09-19 新日本石油株式会社 Lubricating oil composition for metal belt type continuously variable transmission
DE69915804T2 (en) * 1998-11-13 2004-08-26 Japan Energy Corp. OIL COMPOSITION FOR GEARS
JP4038306B2 (en) * 1999-06-15 2008-01-23 東燃ゼネラル石油株式会社 Lubricating oil composition for continuously variable transmission
JP4663843B2 (en) * 2000-03-29 2011-04-06 Jx日鉱日石エネルギー株式会社 Lubricating oil composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4909952A (en) * 1989-01-03 1990-03-20 The Lubrizol Corporation Sulfur-containing polymeric polyesters and additive concentrates and lubricating oils containing same
WO1993021289A1 (en) * 1992-04-15 1993-10-28 Exxon Chemical Patents Inc. Lubricant composition containing mixed friction modifiers
US5851962A (en) * 1992-08-18 1998-12-22 Ethyl Japan Corporation Lubricant composition for wet clutch or wet brake
US5372735A (en) * 1994-02-10 1994-12-13 Ethyl Petroleum Additives, Inc. Automatic transmission fluids and additives therefor
EP0747464A1 (en) * 1995-06-09 1996-12-11 The Lubrizol Corporation A composition for providing anti-shudder friction durability performance for automatic transmissions
WO2000073406A1 (en) * 1999-05-28 2000-12-07 Infineum International Limited Zinc-free continuously variable transmission fluid
US6337309B1 (en) * 1999-05-28 2002-01-08 Infineum International Ltd Zinc-free continuously variable transmission fluid

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273655B2 (en) 1999-04-09 2007-09-25 Shojiro Miyake Slidably movable member and method of producing same
US8152377B2 (en) 2002-11-06 2012-04-10 Nissan Motor Co., Ltd. Low-friction sliding mechanism
US8096205B2 (en) 2003-07-31 2012-01-17 Nissan Motor Co., Ltd. Gear
US8206035B2 (en) 2003-08-06 2012-06-26 Nissan Motor Co., Ltd. Low-friction sliding mechanism, low-friction agent composition and method of friction reduction
US8575076B2 (en) 2003-08-08 2013-11-05 Nissan Motor Co., Ltd. Sliding member and production process thereof
US7771821B2 (en) 2003-08-21 2010-08-10 Nissan Motor Co., Ltd. Low-friction sliding member and low-friction sliding mechanism using same
US7650976B2 (en) 2003-08-22 2010-01-26 Nissan Motor Co., Ltd. Low-friction sliding member in transmission, and transmission oil therefor
EP1508611A2 (en) * 2003-08-22 2005-02-23 Nissan Motor Company, Limited Low-friction sliding member in transmission, and transmission oil therefor
EP1508611A3 (en) * 2003-08-22 2005-11-30 Nissan Motor Company, Limited Low-friction sliding member in transmission, and transmission oil therefor
EP1518921A1 (en) * 2003-09-23 2005-03-30 Afton Chemical Corporation Power transmission fluids having extended friction durability
EP2230292A1 (en) * 2003-11-10 2010-09-22 Afton Chemical Corporation Methods of lubricating transmissions
EP1529831A3 (en) * 2003-11-10 2006-03-15 Afton Chemical Corporation Lubricant compositions for power transmitting fluids
US9267093B2 (en) 2003-11-10 2016-02-23 Afton Chemical Corporation Methods for providing steel-on-steel friction and/or steel-on-paper friction with lubricant compositions for power transmitting fluids
CN1332004C (en) * 2003-11-10 2007-08-15 雅富顿公司 Lubricant compositions for power transmitting fluids
EP1529831A2 (en) * 2003-11-10 2005-05-11 Afton Chemical Corporation Lubricant compositions for power transmitting fluids
AU2004237832B2 (en) * 2003-12-09 2010-01-28 Infineum International Limited Power transmission fluids with improved friction characteristics
EP1541665A1 (en) * 2003-12-09 2005-06-15 Infineum International Limited Power transmission fluids with improved friction characteristics
EP1568759A2 (en) 2004-02-27 2005-08-31 Afton Chemical Corporation Power transmission fluids
US7947636B2 (en) 2004-02-27 2011-05-24 Afton Chemical Corporation Power transmission fluids
EP1568759A3 (en) * 2004-02-27 2008-06-04 Afton Chemical Corporation Power transmission fluids
KR100744983B1 (en) * 2004-10-08 2007-08-02 에프톤 케미칼 코포레이션 Power transmission fluids with enhanced antishudder durability and handling characteristics
EP1645616A1 (en) * 2004-10-08 2006-04-12 Afton Chemical Corporation Power transmission fluids with enhanced antishudder durability
WO2006045044A1 (en) * 2004-10-19 2006-04-27 The Lubrizol Corporation Secondary and tertiary amines as friction modifiers for automatic transmission fluids
EP1739159A3 (en) * 2005-06-30 2009-12-16 Afton Chemical Corporation Methods for improved power transmission performance and lubricating compositions therefor
CN101712906A (en) * 2005-06-30 2010-05-26 雅富顿公司 Methods for improved power transmission performance and compositions therefor
EP1739158A3 (en) * 2005-06-30 2009-12-16 Afton Chemical Corporation Methods for improved power transmission performance and lubricating compositions therefor
EP1739159A2 (en) * 2005-06-30 2007-01-03 Afton Chemical Corporation Methods for improved power transmission performance and lubricating compositions therefor
EP1739321A3 (en) * 2005-06-30 2007-01-10 Afton Chemical Corporation Methods for improved power transmission performance
WO2007121205A3 (en) * 2006-04-12 2007-12-21 Lubrizol Corp Hydroxy-containing tertiary amines as friction modifiers for automatic transmission fluids
CN101421380B (en) * 2006-04-12 2012-05-02 卢布里佐尔公司 Hydroxy-containing tertiary amines as friction modifiers for automatic transmission fluids
WO2007121205A2 (en) * 2006-04-12 2007-10-25 The Lubrizol Corporation Hydroxy-containing tertiary amines as friction modifiers for automatic transmission fluids
GB2439172A (en) * 2006-06-16 2007-12-19 Afton Chemical Corp Power transmission fluid with enhanced friction characteristics
GB2439172B (en) * 2006-06-16 2008-10-08 Afton Chemical Corp Power transmission fluid with enhanced friction characteristics
KR100892893B1 (en) 2006-06-16 2009-04-15 에프톤 케미칼 코포레이션 Power transmission fluid with enhanced friction characteristics
CN105524679A (en) * 2014-09-28 2016-04-27 中国石油化工股份有限公司 Automatic transmission liquid composition and method for improving dynamic friction coefficient of automatic transmission liquid composition
EP3067408A1 (en) * 2015-03-12 2016-09-14 Afton Chemical Corporation Lubricant composition for automatic transmissions
US9469825B2 (en) 2015-03-12 2016-10-18 Afton Chemical Corporation Lubricant composition for automatic transmissions
WO2019073008A1 (en) * 2017-10-11 2019-04-18 Volkswagen Ag Lubricant composition, use for lubricating a transmission system and transmission system
US11578287B1 (en) 2021-12-21 2023-02-14 Afton Chemical Corporation Mixed fleet capable lubricating compositions
US11807827B2 (en) 2022-01-18 2023-11-07 Afton Chemical Corporation Lubricating compositions for reduced high temperature deposits
US11970671B2 (en) 2022-07-15 2024-04-30 Afton Chemical Corporation Detergent systems for oxidation resistance in lubricants
US11912955B1 (en) 2022-10-28 2024-02-27 Afton Chemical Corporation Lubricating compositions for reduced low temperature valve train wear
US11926804B1 (en) 2023-01-31 2024-03-12 Afton Chemical Corporation Dispersant and detergent systems for improved motor oil performance

Also Published As

Publication number Publication date
JP2002275492A (en) 2002-09-25
US20020151441A1 (en) 2002-10-17

Similar Documents

Publication Publication Date Title
EP1233054A1 (en) Automatic transmission fluids with improved anti-shudder properties
US6482778B2 (en) Zinc and phosphorus containing transmission fluids having enhanced performance capabilities
CA2130373C (en) Friction modifier compositions and their use
US8921287B2 (en) Lubricating oil composition
US6617286B2 (en) Lubricating oil composition for continuously variable transmission
US10640723B2 (en) Lubricants containing amine salt of acid phosphate and hydrocarbyl borate
US5972851A (en) Automatic transmission fluids having enhanced performance capabilities
EP1233051A1 (en) Low phosphorus clean gear oil formulations
US20020151443A1 (en) Automatic transmission fluids with improved anti-wear properties
JP5188019B2 (en) Lubricating oil composition
EP3755770B1 (en) Lubricating oils for automatic transmissions
JP2001342484A (en) Lubricating oil composition for automatic transmission
WO2007052826A1 (en) Lubricant composition
EP1239021A2 (en) Power transmission fluids with enhanced lubricating properties
EP1857533A1 (en) Power transmission fluids
AU632936B2 (en) Antioxidant compositions
WO2009113234A1 (en) Lubricating oil composition
CN111615548A (en) Boron-containing automobile gear oil

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20020903

17Q First examination report despatched

Effective date: 20021104

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20021230