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`PATENT APPLICATION TRANSMITTAL FORM
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`SS === Washington, D.C. 20231
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`"PATENT" fr
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`Case Docket No. 20021004 2 =
`= ——
`EL325202599US
`"Express Mail” mailing label number
`. Date of Deposit April 5, 2002. wo ==c
`Thereby certify that this paper or fee is being deposited with the United States Postal Service "Express Mai =n
`Post Office to Addressee" service under 37 CFR 1.10 on the date indicated above and is addressed to thew>=s5
`Assistant Commissioner for Patents, Washington, D.C. 20231.
`ie
`>
`Ly
`
`=v
`
`Regina F. Anginoli
`(Typed or printed name of person mailing paper or fee)
`
`Transmitted herewith for filing is the patent application of
`
`Inventor:
`
`For:
`
`Rolfe J. Hartley, Malcolm Waddoups
`Lubricating Oil Composition
`
`_ Enclosed are:
`
`(X]
`
`Sasso
`
`oreeeeee
`
`[xX]
`ix]
`tJ
`
`[Xx]
`
`Specification and Claims with Declaration;
`Specification and Claims without Declaration;
`sheets of informal drawings;
`sheets of formal drawings;
`An assignmentof the invention to
`The certified copy of a priority application,
`Information Disclosure Statement, Form - 1449;
`Copies ofcitations as listed on attached Form - 1449;
`Preliminary Amendment;
`
`Address all future communicationsto:
`
`Infineum USA L.P.
`Law Department
`1900 East Linden Avenue
`P.O. Box 710
`Linden, New Jersey 07036-0710
`
`[
`
`]
`
`Filed on
`Priority of application Serial No.
`in
`is claimed under 35 USC 119.
`
`(Country)
`
`[Xx]
`
`The Filing Fee is calculated below.
`
`
`
`
`
`CLAIMS AS FILED po
`
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`
`
`
`Lindependentcaims|3=]|xsao|co
`Muitiple Dependent Claim Fee PP
`$280.00
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`potorarecrcs||76.00|
`
`Please charge my Deposit Account No. 05-1710 in the amountof $
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`776.00
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`[X]
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`The Assistant Commissioner is hereby authorized to charge any additional fees which may be
`required during the entire pendency of the application, or credit any overpayment, to Deposit
`Account No. 05-1710. A duplicate copy of this Form is enclosed
`April 5, 2002
`Date of Signature
`
` Attomey or Agent
`
`
`Infineum USA L.P.
`Law Department
`1900 East Linden Avenue
`P.O. Box 710
`Linden, New Jersey 07036-0710
`
`acob M.Levine
`Registration No. 32,509
`Telephone No. (908) 474-2418
`Facsimile No. (908) 474-2431
`
`‘
`(For Internal Use Only: Job Ne. 813,856)
`
`Page 1 of 219
`
`ORONITE EXHIBIT 1004
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`Page 1 of 219
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`ORONITE EXHIBIT 1004
`
`

`

`IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
`
`“LUBRICATING OIL COMPOSITION”
`
`(2002L004)
`
`Inventor(s):
`
`Rolfe J. HARTLEY
`Malcolm WADDOUPS
`
`EL325202599US
`“Express Mail’ mailing label! number
`Date of Deposit
`April 5, 2002
`| hereby certify that this paper or fee is being deposited with the
`United States Postal Service “Express Mail Post Office to Addressee”
`service under 37 CFR 1.10 on the date indicated above and is
`addressed to the Commissioner of Patents and Trademarks,
`Washington, D.C. 20231.
`
`(Typed
`
`Regina F. Anginoli
`inted name of person mailing paper or fee)
`
`
`
`
`
`Page 2 of 219
`
`Page 2 of 219
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`

`

`LUBRICATING OIL COMPOSITION
`
`The present invention relates to lubricating oil compositions. More particularly,
`
`the present invention relates to lubricating oil compositions, which exhibit
`
`simultaneously improved low temperature valve train wear performance, excellent
`
`compatibility with fluoroelastomer materials commonly used for seals in modern
`
`internal combustion engines, and improved fuel economy properties.
`
`BACKGROUND OF THE INVENTION
`
`10
`
`Lubricating oil compositions used to lubricate internal combustion engines
`
`15
`
`20
`
`25
`
`30
`
`contain base oil of lubricating viscosity, or a mixture of such oils, and additives used
`
`to improve the performance characteristics of the oil. For example, additives are used
`
`to improve detergency, to reduce engine wear, to provide stability against heat and
`
`oxidation, to reduce oil consumption, to inhibit corrosion, to act as a dispersant, and to
`
`reduce friction loss. Some additives provide multiple benefits, such as dispersant-
`
`viscosity modifiers. Other additives, while improving one characteristic of the
`
`lubricating oil, have an adverse effect on other characteristics. Thus, to provide
`
`lubricating oil having optimal overall performance, it is necessary to characterize and
`
`understand all the effects of the various additives available, and carefully balance the
`
`additive content of the lubricant.
`
`It has been proposed in many patents and articles (for example, U.S. Patent
`
`No. 4,164,473; 4,176,073; 4,176,074; 4,192,757, 4,248,720; 4,201,683; 4,289,635;
`
`and 4,479,883) that oil-soluble molybdenum compoundsare useful as lubricant
`
`additives. In particular, the addition of molybdenum compoundsto oil, particularly
`
`molybdenum dithiocarbamate compounds, provides the oil with improved boundary
`
`friction characteristics and bench tests demonstrate that the coefficientof friction of
`
`oil containing such molybdenum compoundsis generally lower than thatof oil
`
`containing organic friction modifiers. This reduction in coefficient of friction results
`
`in improved antiwear properties and may contribute to enhanced fuel economyin
`
`gasoline or diesel fired engines, including both short- and long-term fuel economy
`
`properties (i.e., fuel economy retention properties). To provide antiwear effects,
`
`molybdenum compoundsare generally added in amounts introducing from about 350
`
`ppm up to 2,000 ppm of molybdenum into the oil. While molybdenum compounds
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`-2-
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`are effective antiwear agents and may further provide fuel economybenefits, such
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`molybdenum compoundsare expensive relative to more conventional, metal-free
`
`(ashiess) organic friction modifiers
`
`U.S. Patent No. 6,300,291 discloses a lubricating oil composition having a
`
`specified Noack volatility containing a base oil of a specified viscosity index,
`
`calcium-based detergent, zinc dihydrocarbyldithiophosphate (ZDDP) antiwear agent,
`
`a molybdenum compound and a nitrogen-containing friction modifier. The
`
`molybdenum compound wasused in an amount providing the formulated lubricant
`
`10
`
`with up to 350 ppm of molybdenum. The claimed materials are described as
`
`15
`
`20
`
`25
`
`30
`
`providing fuel economy benefits compared to compositions containing only
`‘molybdenum compounds.
`
`Modern internal combustion engines include numerous gaskets and other seals formed
`of fluoroelastomer materials, such as Viton™. Nitrogen-containing additives are
`suspected of, over time, contributing to the deterioration of such materials. Therefore,
`
`it would be desirable to find a lubricating oil composition that provides improved fuel
`
`economy benefit; demonstrates excellent wear protection characteristics, is relatively.
`
`low in cost, and is free of nitrogen-containing friction modifiers.
`
`It has now been found that the addition of small amounts of one or moreoil
`
`soluble molybdenum compounds, in combination with an ashless, organic nitrogen-
`
`free friction modifier, ZDDP. and a calcium detergent provide low cost lubricating oils —
`
`having a demonstrable fuel economy benefit; excellent wear protection
`characteristics, and reduced adverseeffects on engine seals formed of Viton™ and
`similar fluoroelastomers.
`
`The present invention also provides many additional advantages that shall
`
`become apparent as described below.
`
`SUMMARY OF THE INVENTION
`
`In accordance with a first aspect, the invention provides a lubricating oil
`
`composition displaying excellent low temperature valve train wear performance,
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`-3-
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`improved fuel economy retention properties and compatibility with fluoroelastomer-
`based engine seals, which composition comprises an oil of lubricating viscosity
`having a viscosity index (VDofat least 95; a calcium detergent in an amount
`introducing from about 0.05 to about 0.6 wt. % calcium into the composition; an
`amount of a metal dihydrocarbyldithiophosphate compound introducing up to 0.1 wt.
`% (1000 ppm) of phosphorusinto the composition; at least one molybdenum
`compound in an amountsufficient to provide the composition with at least 10 ppm of
`molybdenum; and an effective amountofat least one organic, nitrogen-free, ashless
`friction modifier; the composition having a Noack volatility of less than 15 %.
`
`In accordance with a second aspect, the invention is directed to a method of
`improving the fuel economy,seal life and/or the wear characteristics of an internal
`combustion engine, which method comprises the steps of lubricating an internal
`combustion engine with a lubricating oil composition ofthefirst aspect and operating
`the engine.
`
`In accordance with a third aspect, the invention is directed to the use of a
`lubricating oil composition ofthe first aspect to improve the fuel economy,seal life
`and/or the wear characteristics of an internal combustion engine.
`
`Other and further objects, advantages and features of the present invention will
`be understood by referenceto the following.
`
`10
`
`20
`
`25
`
`30
`
`DESCRIPTION OF THE PREFERRED EMBODIMENTS
`The oil of lubricating viscosity can be at least one oil selected from the group
`consisting of Group I, GroupIL, or GroupIII base stocksorbase oil blends ofthe
`aforementioned base stocks providedthat the viscosity of the base oil or base oil
`blend is at least 95 and allowsfor the formulation of a lubricating oil composition
`having a Noackvolatility, measured by determining the evaporative loss in mass
`percentofan oil after 1 hour at 250°C accordingto the procedure of ASTM D5880, of
`less than 15%. In addition,the oil of lubricating viscosity may be one or more Group
`IV or Group V base stocks or combinations thereof or base oil mixtures containing
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`-4-
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`one or more Group IV or Group V base stocks in combination with one or more
`
`Group I, Group 0 and/or Group III base stocks.
`
`The mostpreferred oils for fuel economyretention, are:
`
`(a)
`
`Base oil blends of Group III base stocks with Group I or Group II base
`
`stocks, where the combination has a viscosity index of at least 110; or
`
`(b)
`
`Group III, IV or V base stocks or base oil blends of more than one
`
`Group III, IV or V base stocks, where the viscosity index is between
`
`about 120 to about 140.
`
`Definitions for the base stocks and baseoils in this invention are the same as
`
`those found in the American Petroleum Institute (API) publication “Engine Oil
`
`Licensing and Certification System”, Industry Services Department, Fourteenth
`
`Edition, December 1996, Addendum 1, December 1998. Said publication categorizes
`base stocks as follows:
`
`a) Group I base stocks contain less than 90 percent saturates and/or greater than 0.03
`
`percent sulfur and have a viscosity index greater than or equal to 80 andless than 120
`
`using the test methods specified in Table E-1.
`
`b) Group II base stocks contain greater than or equal to 90 percent saturates and less
`
`than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to
`80 and less than 120 using the test methods specified in Table E-1.
`
`c) GroupIII base stocks contain greater than or equal to 90 percentsaturates and less
`than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to
`
`10
`
`20
`
`25
`
`120 using the test methods specified in Table E-1.
`
`d) Group IV base stocks are polyalphaolefins (PAO).
`e) Group V base stocks include all other base stocks not included in Group I,II, IH, or
`
`Iv.
`
`30
`
`Page 6 of 219
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`Page 6 of 219
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`

`

`Table E-1 - Analytical Methods for Base Stock
`
`-5-
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`
`
`
`
`
`
`Le
`
`sane
`
`
`asso
`
`
`
`
`
`
`
`
`
`
`10
`
`Forthe lubricating oil compositions of this invention, any suitable oil-soluble
`organo-molybdenum compoundhavingfriction modifying and/or anti-wear properties in
`lubricating oil compositions may be employed. As an example of such oil-soluble
`organo-molybdenum compounds, there may be mentioned the dithiocarbamates,
`dithiophosphates,dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and
`mixtures thereof. Particularly preferred are molybdenum dithiocarbamates,
`
`dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.
`
`The molybdenum compound may be mono-, di-, tri- or tetra-nuclear. Dinuclear
`and trinuclear molybdenum compoundsare preferred. The molybdenum compoundis
`preferably an organo-molybdenum compound. Morepreferably, the molybdenum
`compoundis selected from the group consisting of molybdenum dithiocarbamates
`(MoDTC), molybdenum dithiophosphates, molybdenum dithiophosphinates,
`molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides and
`mixtures thereof. Most preferably, the molybdenum compoundis present as a
`molybdenum dithiocarbamate or a trinuclear organo-molybdenum compound.
`
`20
`
`25
`
`Additionally, the molybdenum compound maybe an acidic molybdenum
`compound. These compoundswill react with a basic nitrogen compound as measured
`by ASTM test D-664 or D-2896 titration procedure andare typically hexavalent.
`Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium
`molybdate, and other alkaline metal molybdates and other molybdenumsalts,e.g.,
`hydrogen sodium molybdate, MoOCl,, MoO2Brm, Mo.03Clg, molybdenum trioxide or
`similar acidic molybdenum compounds. Alternatively, the compositions of the
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`Page 7 of 219
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`Page 7 of 219
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`-6-
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`present invention can be provided with molybdenum by molybdenum/sulfur
`
`complexes of basic nitrogen compoundsas described, for example, in U.S. Patent
`
`Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195
`
`and 4,259,194; and WO 94/06897.
`
`Among the molybdenum compoundsuseful in the compositions of this invention
`
`are organo-molybdenum compoundsofthe formulae
`
`Mo(ROCS>)4 and
`
`Mo(RSCS2)4
`
`15
`
`20
`
`wherein R is an organo groupselected from the group consisting of alkyl, aryl, aralkyl
`
`and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon
`
`atoms and most preferably alkyl of 2 to 12 carbon atoms. Especially preferred are the
`
`dialkyldithiocarbamates of molybdenum.
`
`Oneclass of preferred organo-molybdenum compoundsuseful in the lubricating
`
`compositions of this invention are trinuclear molybdenum compounds, especially those
`
`of the formula Mo3S;,L,Q, and mixtures thereof wherein L are independently selected
`
`ligands having organo groups with a sufficient number of carbon atomsto render the
`‘compoundsoluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q
`
`is selected from the group of neutral electron donating compounds such as water,
`
`amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-
`
`stoichiometric values. At least 21 total carbon atoms should be present amongall the
`
`ligands’ organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
`
`25
`
`The ligands are independently selected from the group of
`
`——xX-——R
`
`Xy-\y—R
`
`Xy
`
`1
`
`"\ UYye y
`
`2
`
`1,
`
`2,
`
`3,
`
`R
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`Page 8 of 219
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`Page 8 of 219
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`

`

`Xy
`
`
`
`Rj>)x5
`
`Ne
`
`and
`
`O-—R,Moe
`
`Xy
`
`X2
`
`O-——R,
`
`and mixtures thereof, wherein X, X), X2, and Y are independently selected from the
`
`group of oxygen and sulfur, and wherein R,, R2, and R are independently selected from
`
`hydrogen and organo groups that may be the sameor different. Preferably, the organo
`
`groups are hydrocarbyl groups such asalkyl (e.g., in which the carbon atom attached to
`
`the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether
`
`groups. More preferably, each ligand has the same hydrocarbyl group.
`
`The term “hydrocarbyl” denotes a substituent having carbon atomsdirectly
`
`attached to the remainder of the ligand and is predominantly hydrocarbyl .in character
`
`within the context of this invention. Such substituents include the following:
`
`1.
`
`Hydrocarbon substituents,that is, aliphatic (for example alkyl or alkenyl), alicyclic
`
`(for example cycloalkyl or cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-
`
`substituted aromatic nuclei and the like, as well as cyclic substituents wherein thering is
`
`completed through another portion ofthe ligand (that is, any two indicated substituents
`
`may together form an alicyclic group).
`
`2.
`
`Substituted hydrocarbon substituents, that is, those containing non-hydrocarbon
`
`groups which,in the context of this invention, do notalter the predominantly
`
`hydrocarbyl character of the substituent. Those skilled in the art will be aware of
`
`suitable groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto,
`
`alkylmercapto,nitro, nitroso, sulfoxy, etc.).
`
`10
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`15
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`20
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`25
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`Page 9 of 219
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`-8-
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`3.
`
`Hetero substituents, that is, substituents which, while predomimantly hydrocarbon
`
`in character within the context of this invention, contain atoms other than carbon present
`
`in a chain or ring otherwise composed of carbon atoms.
`
`Importantly, the organo groups ofthe ligands have a sufficient number of carbon
`
`atoms to render the compound soluble or dispersible in the oil. For example, the number
`
`of carbon atoms in each group will generally range between about 1 to about 100,
`
`preferably from about 1 to about 30, and more preferably between about 4 to about 20.
`
`Preferred ligands include dialkyldithiophosphate, alkylxanthate, and
`
`10
`
`dialkyldithiocarbamate, and of these dialkyldithiocarbamate is more preferred. Organic
`
`ligands containing two or more of the above functionalities are also capable of serving as
`
`ligands and binding to one or moreof the cores. Those skilled in the art will realize that
`
`formation of the compoundsofthe present invention requires selection of ligands having
`
`the appropriate charge to balance the core’s charge.
`
`Compounds having the formula Mo3S;L,Q,to have cationic cores surrounded by
`
`anionic ligands and are represented by structures such as
`
`5/\\,NZ|
`
`
`
`
`
`
`and
`
`20
`
`f|44 |a
`WsXV
`
`<<“
`
`Page 10 of 219
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`Page 10 of 219
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`

`

`-9-
`
`and have net charges of +4. Consequently, in order to solubilize these cores the total
`
`charge amongall the ligands must be -4. Four monoanionic ligands are preferred.
`
`Without wishing to be bound by anytheory,it is believed that two or more trinuclear
`
`cores may be boundor interconnected by means of one or more ligands and the ligands
`
`may be multidentate. This includes the case of a multidentate ligand having multiple
`
`connections to a single core. It is believed that oxygen and/or selenium may be
`
`substituted for sulfur in the core(s).
`
`Oil-soluble or dispersible trinuclear molybdenum compoundscan be prepared by
`
`10
`
`reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as
`
`15
`
`20
`
`(NH,)2Mo38;3.n(H20), where n varies between 0 and 2 and includes non-stoichiometric
`
`values, with a suitable ligand source such as a tetralkylthiuram disulfide. Other oil-
`
`soluble or dispersible trinuclear molybdenum compounds can be formed during a
`
`reaction in the appropriate solvent(s) of a molybdenum source such as of
`
`(NH4)2Mo3833.n(H20), a ligand source such as tetralkylthiuram disulfide,
`
`dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur abstracting agent such as
`
`cyanideions, sulfite ions, or substituted phosphines. Alternatively, a trinuclear
`
`molybdenum-sulfur halide salt such as [M’]2[Mo3S7Ag¢], where M'’ is a counter ion, and A
`
`is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a
`
`dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s)
`
`to form an oil-soluble or dispersible trinuclear molybdenum compound. The appropriate
`
`liquid/solvent may be, for example, aqueousor organic.
`
`A compound's oil solubility or dispersibility may be influenced by the number
`
`of carbon atomsin the ligand’s organo groups. In the compoundsof the present
`
`invention, at least 21 total carbon atoms should be present amongall the ligands’
`
`organo groups. Preferably, the ligand source chosen hasa sufficient numberof
`
`carbon atomsin its organo groups to render the compoundsoluble or dispersible in
`
`the lubricating composition.
`
`25
`
`30
`
`The terms “oil-soluble”or “dispersible” used herein do not necessarily indicate
`
`that the compoundsor additives are soluble, dissolvable, miscible, or capable of being
`
`suspended in the oil in all proportions. These do mean, however,that they are, for
`
`Page 11 of 219
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`

`-10-
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`instance, soluble or stably dispersible in oil to an extent sufficient to exert their
`
`intended effect in the environment in whichthe oil is employed. Moreover, the
`
`additional incorporation of other additives may also permit incorporation of higher
`
`levels of a particular additive, if desired.
`
`The lubricating compositions of the present invention contain the molybdenum
`compoundin an amount providing the composition with at least 10 ppm of
`molybdenum. An amountofat least 10 ppm of molybdenum from a molybdenum
`compoundhas been foundto be effective to provide a fuel economy benefit in
`combination with an ashless, organic nitrogen-free friction modifier. Preferably, the
`molybdenum from a molybdenum compoundis present in an amountof from about
`10 ppm to about 750 ppm, such as 10 ppm to 350 ppm, more preferably from about
`30 ppm to 200 ppm,still more preferably in an amount of from about 50 ppm to about
`100 ppm,based onthetotal weight of the lubricating composition. Because such
`
`molybdenum compoundsalso provide antiwearcredits to lubricating oil
`compositions, the use thereof allows for a reduction in the amount of metal
`dihydrocarbyl dithiophosphate antiwear agent (e.g., ZDDP) employed. Industry
`trends are leading to a reduction in the amount of ZDDP being addedto lubricating
`
`oils to reduce the phosphorous contentof the oil to below 1000 ppm,such as to 250
`ppm to 750 ppm, or 250 ppm to 500 ppm. To provide adequate wear protection in
`such low phosphorouslubricating oil compositions, the molybdenum compound
`should be present in an amount providing at least 50 ppm by mass of molybdenum.
`The amount of molybdenum and/or zinc may be determined by Inductively Coupled
`
`Plasma (ICP) emission spectroscopy using the method described in ASTM D5185.
`
`Organic, ashless (metal-free), nitrogen-free organic friction modifiers useful in
`the lubricating oil compositions of the present invention are known generally and include
`esters formed by reacting carboxylic acids and anhydrides with alkanols. Other useful
`friction modifiers generally include a polar terminal group (e.g. carboxyl or hydroxyl)
`covalently bondedto an oleophilic hydrocarbon chain. Esters of carboxylic acids and
`anhydrides with alkanols are described in US 4,702,850. Examples of other
`conventional organic friction modifiers are described by M.Belzerin the “Journal of
`
`10
`
`15
`20
`
`25
`
`30
`
`Page 12 of 219
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`Page 12 of 219
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`

`

`-il-
`
`Tribology" (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in "Lubrication
`
`Science" (1988), Vol. 1, pp. 3-26.
`
`The organic friction modifier is included in the lubricating oil compositions of
`
`the present invention in an amount effective to allow the composition to reliably pass a
`
`Sequence VIB fuel economytest in combination with the molybdenum compound. For
`
`example, the organic ashless nitrogen-free friction modifier may be added to the
`
`molybdenum-containing lubricating oil composition in an amountsufficient to obtain
`
`a retained fuel economy improvementofat least 1.7% for an SAE 5W-20lubricant,
`
`1.1% for a 5W-30 lubricant, and 0.6% for a 1OW-30 lubricant as measured at 96 hours
`
`(Phase II performance) in the ASTM Sequence VIB Fuel Economy Test. Typically,
`
`to provide the desired effect, the organic ashless nitrogen-free friction modifieris
`
`added in an amount of from about 0.25 wt.% to about 2.0 wt.% (AD), based on the
`
`total weight of the lubricating oil composition. Preferred organic ashless nitrogen-
`
`free friction modifiers are esters; a particularly preferred organic ashless nitrogen-free
`
`friction modifier is glycerol monooleate (GMO).
`
`Ashless aminic friction modifiers excluded from compositions of the present
`
`invention include oil-soluble alkoxylated mono- and di-amines, which improve
`
`boundary layer lubrication, but may contribute to the deterioration over time of
`
`fluoroelastomer seal materials. One commonclass of such metal free, nitrogen-
`
`containing friction modifier comprises ethoxylated amines. These amines are also
`
`excluded when in the form of an adduct or reaction product with a boron compound such
`
`as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
`
`Metal-containing or ash-forming detergents function both as detergents to reduce
`
`or removedeposits and as acid neutralizers or rust inhibitors, thereby reducing wear and
`
`corrosion and extending engine life. Detergents generally comprise a polar head with a
`
`long hydrophobictail, with the polar head comprising a metalsalt ofan acid organic
`
`compound. The salts may contain a substantially stoichiometric amount of the metal in
`
`which they are usually described as normal or neutral salts, and would typically have a
`
`total base number (TBN), as may be measured by ASTM D-2896of from 0 to 80. It is
`
`possible to include large amounts of a metal base by reacting an excess of a metal
`
`10
`
`15
`
`20
`
`25
`
`30
`
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`

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`-12-
`
`compound such as an oxide or hydroxide with an acid gas such as carbon dioxide. The
`
`resulting overbased detergent comprises neutralized detergent as the outer layer of a
`
`metal base (e.g., carbonate) micelle. Such overbased detergents may have a TBN of 150
`
`or greater, and typically from 250 to 450 or more.
`
`Knowndetergents include oil-soluble neutral and overbased sulfonates, phenates,
`
`sulfurized phenates, thiophosphonates, salicylates, and naphthenates and otheroil-
`
`soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g.,
`
`sodium, potassium,lithium, calcium, and magnesium. The most commonly used metals
`
`10
`
`are calcium and magnesium, which may both be present in detergents used in a
`
`
`20
`
`lubricant, and mixtures of calcium and/or magnesium with sodium. Particularly
`
`convenient metal detergents are neutral and overbased calcium sulfonates having TBN
`
`of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized
`
`phenates having TBN of from 50 to 450.
`
`In the present invention, one or more calcium-based detergents are used in an
`
`amount introducing from about 0.05 to about 0.6 wt. % calcium into the composition.
`
`The amount of calcium may be determined by Inductively Coupled Plasma (ICP)
`
`emission spectroscopy using the method described in ASTM D5185. Preferably, the
`
`calcium-based detergent is overbased and the total base numberof the overbased
`
`calcium based detergent is between about 150 to 450. More preferably, the calctum-
`
`based detergent is an overbased calcium sulfonate detergent. The compositions of the
`
`present invention may further include either neutral or overbased magnesium-based
`
`detergents, however, preferably, the lubricating oil compositions of the present
`
`25
`
`invention will be magnesium free.
`
`Metal dihydrocarbyl dithiophosphate antiwear agents that may be addedto the
`
`lubricating oil composition of the present invention comprise dihydrocarby]
`
`dithiophosphate metal salts wherein the metal may be an alkali or alkaline earth metal,
`
`30
`
`or aluminum,lead, tin, molybdenum, manganese,nickel, copper or preferably, zinc.
`
`The zinc salts are most commonly usedin lubricating oil.
`
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`-13-
`
`Dihydrocarbyl dithiophosphate metal salts may be prepared in accordance with
`
`known techniquesbyfirst forming a dihydrecarbyl dithiophosphoric acid (DDPA),
`
`usually by reaction of one or more alcohol or a phenol with P2Ss5 and then neutralizing
`
`5
`
`the formed DDPA with a metal compound. For example, a dithiophosphoric acid
`may be madebyreacting mixtures of primary and secondary alcohols. Alternatively,
`multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one
`
`are entirely secondary in character and the hydrocarbyl groups on the others are
`
`entirely primary in character. To make the metal salt, any basic or neutral metal
`
`compound could be used but the oxides, hydroxides and carbonates are most
`
`10
`
`generally employed. Commercial additives frequently contain an excess of metal due
`
`to the use of an excess of the basic metal compoundin the neutralization reaction.
`
`The preferred zinc dihydrocarby! dithiophosphates (ZDDP)are oil soluble salts
`
`of dihydrocarbyl dithiophosphoric acids and may be represented by the following
`
`15
`
`formula:
`
`S
`
`RONI
`
`P—s
`
`zn
`
`/
`R'O
`
`2
`
`
`
`
`wherein R and R’ maybe the sameor different hydrocarbyl radicals containing from
`
`1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl,
`
`aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R’
`20~~groups are alkyl groups of 2 to 8 carbon atoms. Thus,the radicals may, for example,
`be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl,
`
`decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl,
`
`methylcyclopentyl, propenyl, butenyl. In order to obtain oil solubility; the total
`
`numberof carbon atoms(i.e. R and R’) in the dithiophosphoric acid will generally be
`
`25
`
`about 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise
`
`zinc dialkyl dithiophosphates.
`
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`-14-
`
`To limit the amount of phosphorusintroduced into the lubricating oil
`
`composition by ZDDPto no more than 0.1 wt. % (1000 ppm), the ZDDP should
`
`preferably be addedto the lubricating oil compositions in amounts no greater than
`
`from about1.1 to 1.3 wt. %, based upon the total weightof the lubricatingoil
`composition.
`
`Other additives, such as the following, may also be presentin lubricating oil
`
`compositions of the present invention.
`
`10
`
`20
`
`Ashless dispersants comprise an oil soluble polymeric hydrocarbon backbone
`
`having functional groups that are capable of associating with particles to be dispersed.
`
`Typically, the dispersants comprise amine, alcohol, amide, or ester polar moieties
`
`attached to the polymer backboneoften via a bridging group. The ashless dispersants
`
`may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides,
`
`and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or
`their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain
`aliphatic hydrocarbons having a polyamineattached directly thereto; and Mannich
`
`condensation products formed by condensing a long chain substituted phenol with
`
`formaldehyde and a polyalkylene polyamine.
`
`Viscosity modifiers (VM) function to impart high and low temperature operability
`
`to a lubricating oil. The VM used may have that sole function, or may be
`
`multifunctional.
`
`Multifunctional viscosity modifiers that also function as dispersants are also
`
`known. Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and
`
`propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates,
`
`methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl
`
`compound,inter polymers of styrene and acrylic esters, and partially hydrogenated
`
`30
`
`copolymers of styrene/ isoprene, styrene/butadienec, and isoprene/butadiene, as well as
`
`the partially hydrogenated homopolymers of butadiene and isoprene and
`
`isoprene/divinylbenzene.
`
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`-15-
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`Oxidation inhibitors or antioxidants reduce the tendencyof base stocks to
`deteriorate in service whichdeterioration can be evidenced by the products of oxidation
`suchas sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
`Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of
`alkylphenolthioesters having preferably Cs to C)2 alkyl side chains, calcium nonylphenol
`sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or
`sulfurized hydrocarbons, phosphorusesters, metal thiocarbamatesandoil soluble copper
`compoundsas described in U.S. 4,867,890.
`
`Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene
`polyols andesters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids
`may be used.
`
`Copperand lead bearing corrosion inhibitors may be used, but are typically not
`required with the formulation ofthe present invention. Typically such compoundsare
`the thiadiazole polysulfides containing from 5 to 50 carbon atoms,their derivatives and
`
`polymers thereof. Derivatives of 1,3,4 thiadiazoles such as those described in U.S.
`
`Patent Nos. 2,719,125; 2,719,126; and 3,087,932;are typical. Other similar materials
`are described in U.S. Patent Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059;
`4,136,043; 4,188,299; and 4,193,882. Other additives are the thio and polythio
`sulfenamidesof thiadiazoles such as those described in U