Lubricant compositions

Abstract: Gear oils and gear oil additive concentrates of enhanced positraction performance are described. They comprise: (i) at least one oil-soluble sulfur-containing extreme pressure or antiwear agent; (ii) at least one oil-soluble amine salt of a partial ester of an acid of phosphorus; and (iii) at least one oil-soluble succinimide of the formula where R₁ is an alkyl or alkenyl group having an average of 8 to 50 carbon atoms, and each of R₂, R₃ and R₄ is a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms. These compositions preferably contain one, more preferably two, and most preferably all three of the following additional components: (iv) at least one amine salt of a carboxylic acid; (v) at least one nitrogen-containing ashless dispersant; and (vi) at least one trihydrocarbyl ester of a pentavalent acid of phosphorus.

Description: This invention relates to additive compositions adapted for use in manual transmission oils and in gear oils, and especially in rear axle lubricants to minimize noise and vibration that occasionally develop in limited slip axles. This invention also relates to manual transmission and gear oils containing such additive compositions. Although a substantial number of gear oil additive concentrates are available in the marketplace, there exists a need for an additive to provide limited slip or enhanced positraction performance in a wide range of mineral and synthetic base gear oils. A most welcome contribution to the art would be the provision of an additive composition enabling present-day gear oil formulations to exhibit improved positraction performance in the GM limited slip axle chatter test (R-4A1-4), commonly referred to as the "big wheel, little wheel test". Inasmuch as gear oils and manual transmission oils (collectively referred to hereinafter in the specification and in the claims as "gear oils") are subjected to prolonged usage in differentials and like devices, it is also important to provide additive systems capable of rendering improved service for long periods of time. This invention provides additive compositions and gear oils capable of suppressing noise and vibration tending to occur in limited slip axles. Additionally, this invention provides additive systems capable of improving the performance of gear oils for long periods of time. In one of its embodiments this invention provides a gear oil additive concentrate which comprises: (i) at least one oil-soluble sulfur-containing extreme pressure or antiwear agent; (ii) at least one oil-soluble amine salt of a partial ester of an acid of phosphorus; (iii) at least one oil-soluble succinimide of the formula wherein R₁ is an alkyl or alkenyl group having an average of 8 to 50 carbon atoms, and each of R₂, R₃ and R₄ is, independently, a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms; and (iv) at least one oil-soluble fully esterified hydrocarbyl ester of phosphoric acid or phosphorothioic acid of the formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom. The proportion of (i):(ii):(iii) on a weight basis are as follows: Component Preferred Range More Preferred Range Most Preferred Range (i) 1 - 5 1.5 - 4.5 2 - 4 (ii) 0.1 - 3 0.2 - 2 0.3 - 1 (iii) 0.05 - 4 0.1 - 2 0.2 - 1 Another embodiment of this invention is a gear oil composition comprising a major amount of a gear oil base stock containing a minor effective amount of components (i), (ii), (iii) and (iv) as above described. Preferred gear oil additive concentrates and gear oil lubricant compositions are those additionally containing (v) at least one oil-soluble amine salt of a carboxylic acid; or (vi) at least one oil-soluble nitrogen-containing ashless dispersant. More preferred are gear oil additive concentrates and gear oil lubricant compositions additionally containing both (v) at least one oil-soluble amine salt of a carboxylic acid, and (vi) at least one oil-soluble nitrogen-containing ashless dispersant. Especially preferred are the gear oil additive concentrates and gear oil lubricant compositions which contain all of components (i), (ii), (iii), (iv), (v) and (vi). Additional highly preferred embodiments of this invention comprise each and every one of the compositions referred to hereinabove which are further characterized by being substantially devoid of any metal-containing additive component. Besides enabling the achievement of desirable positraction performance, such essentially metal-free compositions make possible the provision of gear oils satisfying the requirements of the GL5 classification of the American Petroleum Institute. Thus the preferred lubricant compositions of this invention do not contain such metal-containing additives as the zinc dihydrocarbyldithiophosphates or the sulfonates, phenates and/or sulfurized phenates of the alkali metals or of the alkaline earth metals, components which are almost universally employed in engine oils. Component (i) A wide variety of sulfur-containing extreme pressure or antiwear agents are available for use in the practice of this invention. Among suitable compositions for this use are included sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins (see for example U.S. Pat. Nos. 2,995,569; 3,673,090; 3,703,504; 3,703,505; 3,796,661; 3,873,545; 4,119,549; 4,119,550; 4,147,640; 4,191,659; 4,240,958; 4,344,854; 4,472,306; and 4,711,736), dihydrocarbyl polysulfides (see for example U.S. Pat. Nos. 2,237,625; 2,237,627; 2,527,948; 2,695,316; 3,022,351; 3,308,166; 3,392,201; 4,564,709; and British 1,162,334), sulfurized Diels-Alder adducts (see for example U.S. Pat. Nos. 3,632,566; 3,498,915; and Re 27,331), sulfurized dicyclopentadiene (see for example U.S. Pat. Nos. 3,882,031 and 4,188,297), sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefin (see for example U.S. Pat. Nos. 4,149,982; 4,166,796; 4,166,797; 4,321,153 and 4,481,140), co-sulfurized blends of fatty acid, fatty acid ester and α-olefin (see for example U.S. Pat. No. 3,953,347), functionally-substituted dihydrocarbyl polysulfides (see for example U.S. Pat. No. 4,218,332), thia-aldehydes, thia-ketones and derivatives thereof (e.g. acids, esters, imines, or lactones) (see for example U.S. Pat. No. 4,800,031; and International Application Publication No. WO 88/03552), epithio compounds (see for example U.S. 4,217,233), sulfur-containing acetal derivatives (see for example U.S. Pat. No. 4,248,723), co-sulfurized blends of terpene and acyclic olefins (see for example U.S. 4,584,113), sulfurized borate compounds (see for example U.S. 4,701,274), and polysulfide olefin products (see for example U.S. 4,795,576). Preferred materials useful as component (i) are sulfur-containing organic compounds in which the sulfur-containing species are bound directly to carbon or to more sulfur. One particularly preferred class of such agents is made by reacting an olefin such as isobutene with sulfur. The product, e.g., sulfurized isobutene, typically has a sulfur content of 10 to 50%, preferably 30 to 50%, by weight. A wide variety of other olefins or unsaturated hydrocarbons, e.g., isobutene dimer or trimer, may be used to form such agents. Another particularly preferred class of such agents is composed of one or more compounds represented by the formula R - S x - R' where R and R' are hydrocarbyl groups each of which preferably contains 3 to 18 carbon atoms and x is preferably in the range of from 2 to 8, and more preferably in the range of from 2 to 5. The hydrocarbyl groups can be of widely varying types such as alkyl, cycloalkyl, alkenyl, aryl, or aralkyl. Tertiary alkyl polysulfides such as di-tert-butyl trisulfide, and mixtures comprising di-tert-butyl trisulfide (e.g. a mixture composed principally or entirely of the tri-, tetra-, and pentasulfides) are preferred. Examples of other useful dihydrocarbyl polysulfides include the diamyl polysulfides, the dinonyl polysulfides, the didodecyl polysulfides, and the dibenzyl polysulfides, among others. Other particularly preferred sulfur-containing extreme pressure agent which may be used in the compositions of the invention are the sulfur- and phosphorus-containing additives already mentioned, especially the thiophosphates, dithiophosphates, trithiophosphates and tetrathiophosphates, e.g., the fully or partially esterified hydrocarbyl esters of the mono-, di-, tri-, and tetrathiophosphoric acids, and the amine salts of the partially esterified mono-, di-, tri-, and tetrathiophosphoric acids. The aforesaid hydrocarbyl groups may each typically contain 2 to 30, preferably 4 to 12, carbon atoms each. Component (ii) Component (ii) is composed of one or more oil-soluble amine salts of one or more partial esters of one or more acids of phosphorus, preferably one or more partial esters of one or more acids of pentavalent phosphorus. Such compounds may be represented by the formulas or mixtures thereof. In Formulas I, II and III, each of R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ is, independently, a hydrocarbyl group and each of X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, X⁹, X¹⁰, X¹¹, and X¹² is independently, an oxygen atom or a sulfur atom. Suitable salts or amine adducts of the above partially esterified acids of pentavalent phosphorus include such compounds as: Octylamine salt of O-monobutylphosphoric acid Octylamine salt of O,O-dibutylphosphoric acid Octylamine salt of S-monobutylthiophosphoric acid Octylamine salt of O-monobutylthiophosphoric acid Octylamine salt of O,S-dibutylthiophosphoric acid Octylamine salt of O,O-dibutylthiophosphoric acid Octylamine salt of O,S-dibutyldithiophosphoric acid Octylamine salt of S,S-dibutyldithiophosptioric acid Octylamine salt of O-monobutyldithiophosphoric acid Octylamine salt of S-monobutyldithiophosphoric acid Octylamine salt of S-monobutyltrithiophosphoric acid Octylamine salt of S,S-dibutyltrithiophosphoric acid Octylamine salt of O-monobutylthionophosphoric acid Octylamine salt of O,O-dibutylthionophosphoric acid Octylamine salt of S-monobutylthiothionophosphoric acid Octylamine salt of O-monobutylthiothionophosphoric acid Octylamine salt of O,S-dibutylthiothionophosphoric acid Octylamine salt of O,O-dibutylthiothionophosphoric acid Octylamine salt of O,S-dibutyldithiothionophosphoric acid Octylamine salt of S,S-dibutyldithiothionophosphoric acid Octylamine salt of O-monobutyldithiothionophosphoric acid Octylamine salt of S-monobutyldithiothionophosphoric acid Octylamine salt of S-monobutyltrithiothionosphoric acid Octylamine salt of S,S-dibutyltrithiothionophosphoric acid Octylamine salt of O-monoamylphosphoric acid Octylamine salt of O,O-diamylphosphoric acid Octylamine salt of S-monoamylthiophosphoric acid Octylamine salt of O-monoamylthiophosphoric acid Octylamine salt of O,S-diamylthiophosphoric acid Octylamine salt of O,O-diamylthiophosphoric acid Octylamine salt of O,S-diamyldithiophosphoric acid Octylamine salt of S,S-diamyldithiophosphoric acid Octylamine salt of O-monoamyldithiophosphoric acid Octylamine salt of S-monoamyldithiophosphoric acid Octylamine salt of S-monoamyltrithiophosphoric acid Octylamine salt of S,S-diamyltrithiophosphoric acid Octylamine salt of O-monoamylthionophosphoric acid Octylamine salt of O,O-diamylthionophosphoric acid Octylamine salt of S-monoamylthiothionophosphoric acid Octylamine salt of O-monoamylthiothionophosphoric acid Octylamine salt of O,S-diamylthiothionophosphoric acid Octylamine salt of O,O-diamylthiothionophosphoric acid Octylamine salt of O,S-diamyldithiothionophosphoric acid Octylamine salt of S,S-diamyldithiothionophosphoric acid Octylamine salt of O-monoamyldithiothionophosphoric acid Octylamine salt of S-monoamyldithiothionophosphoric acid Octylamine salt of S-monoamyltrithiothionosphoric acid Octylamine salt of S,S-diamyltrithiothionophosphoric acid Octylamine salt of O-monohexylphosphoric acid Octylamine salt of O,O-dihexylphosphoric acid Octylamine salt of S-monohexylthiophosphoric acid Octylamine salt of O-monohexylthiophosphoric acid Octylamine salt of O,S-dihexylthiophosphoric acid Octylamine salt of O,O-dihexylthiophosphoric acid Octylamine salt of O,S-dihexyldithiophosphoric acid Octylamine salt of S,S-dihexyldithiophosphoric acid Octylamine salt of O-monohexyldithiophosphoric acid Octylamine salt of S-monohexyldithiophosphoric acid Octylamine salt of S-monohexyltrithiophosphoric acid Octylamine salt of S,S-dihexyltrithiophosphoric acid Octylamine salt of O-monohexylthionophosphoric acid Octylamine salt of O,O-dihexylthionophosphoric acid Octylamine salt of S-monohexylthiothionophosphoric acid Octylamine salt of O-monohexylthiothionophosphoric acid Octylamine salt of O,S-dihexylthiothionophosphoric acid Octylamine salt of O,O-dihexylthiothionophosphoric acid Octylamine salt of O,S-dihexyldithiothionophosphoric acid Octylamine salt of S,S-dihexyldithiothionophosphoric acid Octylamine salt of O-monohexyldithiothionophosphoric acid Octylamine salt of S-monohexyldithiothionophosphoric acid Octylamine salt of S-monohexyltrithiothionosphoric acid Octylamine salt of S,S-dihexyltrithiothionophosphoric acid Octylamine salt of O-monoheptylphosphoric acid Octylamine salt of O,O-diheptylphosphoric acid Octylamine salt of S-monoheptylthiophosphoric acid Octylamine salt of O-monoheptylthiophosphoric acid Octylamine salt of O,S-diheptylthiophosphoric acid Octylamine salt of O,O-diheptylthiophosphoric acid Octylamine salt of O,S-diheptyldithiophosphoric acid Octylamine salt of S,S-diheptyldithiophosphoric acid Octylamine salt of O-monoheptyldithiophosphoric acid Octylamine salt of S-monoheptyldithiophosphoric acid Octylamine salt of S-monoheptyltrithiophosphoric acid Octylamine salt of S,S-diheptyltrithiophosphoric acid Octylamine salt of O-monoheptylthionophosphoric acid Octylamine salt of O,O-diheptylthionophosphoric acid Octylamine salt of S-monoheptylthiothionophosphoric acid Octylamine salt of O-monoheptylthiothionophosphoric acid Octylamine salt of O,S-diheptylthiothionophosphoric acid Octylamine salt of O,O-diheptylthiothionophosphoric acid Octylamine salt of O,S-diheptyldithiothionophosphoric acid Octylamine salt of S,S-diheptyldithiothionophosphoric acid Octylamine salt of O-monoheptyldithiothionophosphoric acid Octylamine salt of S-monoheptyldithiothionophosphoric acid Octylamine salt of S-monoheptyltrithiothionosphoric acid Octylamine salt of S,S-diheptyltrithiothionophosphoric acid Octylamine salt of O-mono-2-ethylhexylphosphoric acid Octylamine salt of O,O-di-2-ethylhexylphosphoric acid Octylamine salt of S-mono-2-ethylhexylthiophosphoric acid Octylamine salt of O-mono-2-ethylhexylthiophosphoric acid Octylamine salt of O,S-di-2-ethylhexylthiophosphoric acid Octylamine salt of O,O-di-2-ethylhexylthiophosphoric acid Octylamine salt of O,S-di-2-ethylhexyldithiophosphoric acid Octylamine salt of S,S-di-2-ethylhexyldithiophosphoric acid Octylamine salt of O-mono-2-ethylhexyldithiophosphoric acid Octylamine salt of S-mono-2-ethylhexyldithiophosphoric acid Octylamine salt of S-mono-2-ethylhexyltrithiophosphoric acid Octylamine salt of S,S-di-2-ethylhexyltrithiophosphoric acid Octylamine salt of O-mono-2-ethylhexylthionophosphoric acid Octylamine salt of O,O-di-2-ethylhexylthionophosphoric acid Octylamine salt of S-mono-2-ethylhexylthiothionophosphoric acid Octylamine salt of O-mono-2-ethylhexylthiothionophosphoric acid Octylamine salt of O,S-di-2-ethylhexylthiothionophosphoric acid Octylamine salt of O,O-di-2-ethylhexylthiothionophosphoric acid Octylamine salt of O,S-di-2-ethylhexyldithiothionophosphoric acid Octylamine salt of S,S-di-2-ethylhexyldithiothionophosphoric acid Octylamine salt of O-mono-2-ethylhexyldithiothionophosphoric acid Octylamine salt of S-mono-2-ethylhexyldithiothionophosphoric acid Octylamine salt of S-mono-2-ethylhexyltrithiothionosphoric acid Octylamine salt of S,S-di-2-ethylhexyltrithiothionophosphoric acid Octylamine salt of O-monodecylphosphoric acid Octylamine salt of O,O-didecylphosphoric acid Octylamine salt of S-monodecylthiophosphoric acid Octylamine salt of O-monodecylthiophosphoric acid Octylamine salt of O,S-didecylthiophosphoric acid Octylamine salt of O,O-didecylthiophosphoric acid Octylamine salt of O,S-didecyldithiophosptioric acid Octylamine salt of S,S-didecyldithiophosphoric acid Octylamine salt of O-monodecyldithiophosphoric acid Octylamine salt of S-monodecyldithiophosphoric acid Octylamine salt of S-monodecyltrithiophosphoric acid Octylamine salt of S,S-didecyltrithiophosphoric acid Octylamine salt of O-monodecylthionophosphoric acid Octylamine salt of O,O-didecylthionophosphoric acid Octylamine salt of S-monodecylthiothionophosphoric acid Octylamine salt of O-monodecylthiothionophosphoric acid Octylamine salt of O,S-didecylthiothionophosphoric acid Octylamine salt of O,O-didecylthiothionophosphoric acid Octylamine salt of O,S-didecyldithiothionophosphoric acid Octylamine salt of S,S-didecyldithiothionophosphoric acid Octylamine salt of O-monodecyldithiothionophosphoric acid Octylamine salt of S-monodecyldithiothionophosphoric acid Octylamine salt of S-monodecyltrithiothionosphoric acid Octylamine salt of S,S-didecyltrithiothionophosphoric acid Octylamine salt of O-monododecylphosphoric acid Octylamine salt of O,O-didodecylphosphoric acid Octylamine salt of S-monododecylthiophosphoric acid Octylamine salt of O-monododecylthiophosphoric acid Octylamine salt of O,S-didodecylthiophosphoric acid Octylamine salt of O,O-didodecylthiophosphoric acid Octylamine salt of O,S-didodecyldithiophosphoric acid Octylamine salt of S,S-didodecyldithiophosphoric acid Octylamine salt of O-monododecyldithiophosphoric acid Octylamine salt of S-monododecyldithiophosphoric acid Octylamine salt of S-monododecyltrithiophosphoric acid Octylamine salt of S,S-didodecyltrithiophosphoric acid Octylamine salt of O-monododecylthionophosphoric acid Octylamine salt of O,O-didodecylthionophosphoric acid Octylamine salt of S-monododecylthiothionophosphoric acid Octylamine salt of O-monododecylthiothionophosphoric acid Octylamine salt of O,S-didodecylthiothionophosphoric acid Octylamine salt of O,O-didodecylthiothionophosphoric acid Octylamine salt of O,S-didodecyldithiothionophosphoric acid Octylamine salt of S,S-didodecyldithiothionophosphoric acid Octylamine salt of O-monododecyldithiothionophosphoric acid Octylamine salt of S-monododecyldithiothionophosphoric acid Octylamine salt of S-monododecyltrithiothionosphoric acid Octylamine salt of S,S-didodecyltrithiothionophosphoric acid Octylamine salt of O-monotetradecylphosphoric acid Octylamine salt of O,O-ditetradecylphosphoric acid Octylamine salt of S-monotetradecylthiophosphoric acid Octylamine salt of O-monotetradecylthiophosphoric acid Octylamine salt of O,S-ditetradecylthiophosphoric acid Octylamine salt of O,O-ditetradecylthiophosphoric acid Octylamine salt of O,S-ditetradecyldithiophosphoric acid Octylamine salt of S,S-ditetradecyldithiophosphoric acid Octylamine salt of O-monotetradecyldithiophosphoric acid Octylamine salt of S-monotetradecyldithiophosphoric acid Octylamine salt of S-monotetradecyltrithiophosphoric acid Octylamine salt of S,S-ditetradecyltrithiophosphoric acid Octylamine salt of O-monotetradecylthionophosphoric acid Octylamine salt of O,O-ditetradecylthionophosphoric acid Octylamine salt of S-monotetradecylthiothionophosphoric acid Octylamine salt of O-monotetradecylthiothionophosphoric acid Octylamine salt of O,S-ditetradecylthiothionophosphoric acid Octylamine salt of O,O-ditetradecylthiothionophosphoric acid Octylamine salt of O,S-ditetradecyldithiothionophosphoric acid Octylamine salt of S,S-ditetradecyldithiothionophosphoric acid Octylamine salt of O-monotetradecyldithiothionophosphoric acid Octylamine salt of S-monotetradecyldithiothionophosphoric acid Octylamine salt of S-monotetradecyltrithiothionosphoric acid Octylamine salt of S,S-ditetradecyltrithiothionophosphoric acid Octylamine salt of O-monotetradecylphosphoric acid Octylamine salt of O,O-ditetradecylphosphoric acid Octylamine salt of S-monotetradecylthiophosphoric acid Octylamine salt of O-monotetradecylthiophosphoric acid Octylamine salt of O,S-ditetradecylthiophosphoric acid Octylamine salt of O,O-ditetradecylthiophosphoric acid Octylamine salt of O,S-ditetradecyldithiophosphoric acid Octylamine salt of S,S-ditetradecyldithiophosphoric acid Octylamine salt of O-monotetradecyldithiophosphoric acid Octylamine salt of S-monotetradecyldithiophosphoric acid Octylamine salt of S-monotetradecyltrithiophosphoric acid Octylamine salt of S,S-ditetradecyltrithiophosphoric acid Octylamine salt of O-monotetradecylthionophosphoric acid Octylamine salt of O,O-ditetradecylthionophosphoric acid Octylamine salt of S-monotetradecylthiothionophosphoric acid Octylamine salt of O-monotetradecylthiothionophosphoric acid Octylamine salt of O,S-ditetradecylthiothionophosphoric acid Octylamine salt of O,O-ditetradecylthiothionophosphoric acid Octylamine salt of O,S-ditetradecyldithiothionophosphoric acid Octylamine salt of S,S-ditetradecyldithiothionophosphoric acid Octylamine salt of O-monotetradecyldithiothionophosphoric acid Octylamine salt of S-monotetradecyldithiothionophosphoric acid Octylamine salt of S-monotetradecyltrithiothionosphoric acid Octylamine salt of S,S-ditetradecyltrithiothionophosphoric acid Octylamine salt of O-monohexadecylphosphoiic acid Octylamine salt of O,O-dihexadecylphosphoric acid Octylamine salt of S-monohexadecylthiophosphoric acid Octylamine salt of O-monohexadecylthiophosphoric acid Octylamine salt of O,S-dihexadecylthiophosphoric acid Octylamine salt of O,O-dihexadecylthiophosphoric acid Octylamine salt of O,S-dihexadecyldithiophosphoric acid Octylamine salt of S,S-dihexadecyldithiophosphoric acid Octylamine salt of O-monohexadecyldithiophosphoric acid Octylamine salt of S-monohexadecyldithiophosphoric acid Octylamine salt of S-monohexadecyltrithiophosphoric acid Octylamine salt of S,S-dihexadecyltrithiophosphoric acid Octylamine salt of O-monohexadecylthionophosphoric acid Octylamine salt of O,O-dihexadecylthionophosphoric acid Octylamine salt of S-monohexadecylthiothionophosphoric acid Octylamine salt of O-monohexadecylthiothionophosphoric acid Octylamine salt of O,S-dihexadecylthiothionophosphoric acid Octylamine salt of O,O-dihexadecylthiothionophosphoric acid Octylamine salt of O,S-dihexadecyldithiothionophosphoric acid Octylamine salt of S,S-dihexadecyldithiothionophosphoric acid Octylamine salt of O-monohexadecyldithiothionophosphoric acid Octylamine salt of S-monohexadecyldithiothionophosphoric acid Octylamine salt of S-monohexadecyltrithiothionosphoric acid Octylamine salt of S,S-dihexadecyltrithiothionophosphoric acid Octylamine salt of O-monooctadecylphosphoric acid Octylamine salt of O,O-dioctadecylphosphoric acid Octylamine salt of S-monooctadecylthiophosphoric acid Octylamine salt of O-monooctadecylthiophosphoric acid Octylamine salt of O,S-dioctadecylthiophosphoric acid Octylamine salt of O,O-dioctadecylthiophosphoric acid Octylamine salt of O,S-dioctadecyldithiophosphoric acid Octylamine salt of S,S-dioctadecyldithiophosphoric acid Octylamine salt of O-monooctadecyldithiophosphoric acid Octylamine salt of S-monooctadecyldithiophosphoric acid Octylamine salt of S-monooctadecyltrithiophosphoric acid Octylamine salt of S,S-dioctadecyltrithiophosphoric acid Octylamine salt of O-monooctadecylthionophosphoric acid Octylamine salt of O,O-dioctadecylthionophosphoric acid Octylamine salt of S-monooctadecylthiothionophosphoric acid Octylamine salt of O-monooctadecylthiothionophosphoric acid Octylamine salt of O,S-dioctadecylthiothionophosphoric acid Octylamine salt of O,O-dioctadecylthiothionophosphoric acid Octylamine salt of O,S-dioctadecyldithiothionophosphoric acid Octylamine salt of S,S-dioctadecyldithiothionophosphoric acid Octylamine salt of O-monooctadecyldithiothionophosphoric acid Octylamine salt of S-monooctadecyldithiothionophosphoric acid Octylamine salt of S-monooctadecyltrithiothionosphoric acid Octylamine salt of S,S-dioctadecyltrithiothionophosphoric acid Octylamine salt of O-monooleylphosphoric acid Octylamine salt of O,O-dioleylphosphoric acid Octylamine salt of S-monooleylthiophosphoric acid Octylamine salt of O-monooleylthiophosphoric acid Octylamine salt of O,S-dioleylthiophosphoric acid Octylamine salt of O,O-dioleylthiophosphoric acid Octylamine salt of O,S-dioleyldithiophosphoric acid Octylamine salt of S,S-dioleyldithiophosphoric acid Octylamine salt of O-monooleyldithiophosphoric acid Octylamine salt of S-monooleyldithiophosphoric acid Octylamine salt of S-monooleyltrithiophosphoric acid Octylamine salt of S,S-dioleyltrithiophosphoric acid Octylamine salt of O-monooleylthionophosphoric acid Octylamine salt of O,O-dioleylthionophosphoric acid Octylamine salt of S-monooleylthiothionophosphoric acid Octylamine salt of O-monooleylthiothionophosphoric acid 2Octylamine salt of O,S-dioleylthiothionophosphoric acid Octylamine salt of O,O-dioleylthiothionophosphoric acid Octylamine salt of O,S-dioleyldithiothionophosphoric acid Octylamine salt of S,S-dioleyldithiothionophosphoric acid Octylamine salt of O-monooleyldithiothionophosphoric acid Octylamine salt of S-monooleyldithiothionophosphoric acid Octylamine salt of S-monooleyltrithiothionosphoric acid Octylamine salt of S,S-dioleyltrithiothionophosphoric acid Octylamine salt of O-monobenzylphosphoric acid Octylamine salt of O,O-dibenzylphosphoric acid Octylamine salt of S-monomethylcyclohexylthiophosphoric acid Octylamine salt of O-monomethylcyclohexylthiophosphoric acid Octylamine salt of O,S-dibenzylthiophosphoric acid Octylamine salt of O,O-dimethylcyclohexylthiophosphoric acid Octylamine salt of O,S-dibenzyldithiophosphoric acid Octylamine salt of S,S-dibenzyldithiophosphoric acid Octylamine salt of O-monomethylcyclohexyldithiophosphoric acid Octylamine salt of S-monobenzyldithiophosphoric acid Octylamine salt of S-monomethylcyclohexyltrithiophosphoric acid Octylamine salt of S,S-dibenzyltrithiophosphoric acid Octylamine salt of O-monomethylcyclohexylthionophosphoric acid Octylamine salt of O,O-dimethylcyclohexylthionophosphoric acid Octylamine salt of S-monobenzylthiothionophosphoric acid Octylamine salt of O-monobenzylthiothionophosphoric acid Octylamine salt of O,S-dimethylcyclohexylthiothionophosphoric acid Octylamine salt of O,O-dimethylcyclohexylthiothionophosphoric acid Octylamine salt of O,S-dibenzyldithiothionophosphoric acid Octylamine salt of S,S-dibenzyldithiothionophosphoric acid Octylamine salt of O-monomethylcyclohexyldithiothionophosphoric acid Octylamine salt of S-monomethylcyclohexyldithiothionophosphoric acid Octylamine salt of S-monomethylcyclohexyltrithiothionosphoric acid Octylamine salt of S,S-dibenzyltrithiothionophosphoric acid Octylamine salt of O-monoxylylphosphoric acid Octylamine salt of O,O-ditolylphosphoric acid Octylamine salt of S-monotolylthiophosphoric acid Octylamine salt of O-monoxylylthiophosphoric acid Octylamine salt of O,S-ditolylthiophosphoric acid Octylamine salt of O,O-dixylylthiophosphoric acid Octylamine salt of O,S-dixylyldithiophosphoric acid Octylamine salt of S,S-ditolyldithiophosphoric acid Octylamine salt of O-monoxylyldithiophosphoric acid Octylamine salt of S-monotolyldithiophosphoric acid Octylamine salt of S-monoxylyltrithiophosphoric acid Octylamine salt of S,S-dixylyltrithiophosphoric acid Octylamine salt of O-monotolylthionophosptioric acid Octylamine salt of O,O-dixylylthionophosphoric acid Octylamine salt of S-monoxylylthiothionophosphoric acid Octylamine salt of O-monotolylthiothionophosphoric acid Octylamine salt of O,S-dixylylthiothionophosphoric acid Octylamine salt of O,O-ditolylthiothionophosphoric acid Octylamine salt of O,S-dixylyldithiothionophosphoric acid Octylamine salt of S,S-ditolyldithiothionophosphoric acid Octylamine salt of O-monoxylyldithiothionophosphoric acid Octylamine salt of S-monotolyldithiothionophosphoric acid Octylamine salt of S-monotolyltrithiothionosphoric acid Octylamine salt of S,S-ditolyltrithiothionophosphoric acid Octylamine salt of O-isopropyl-O-octadecylphosphoric acid Octylamine salt of O-nonyl-S-butylthiophosphoric acid Octylamine salt of O-undecyl-O-methylthiophosphoric acid Octylamine salt of O-cyclohexyl-S-decyldithiophosphoric acid Octylamine salt of S-phenyl-S-tetradecyldithiophosphoric acid Octylamine salt of S-pentadecyl-S-cyclohexenyltrithiophosphoric acid Octylamine salt of O-ethyl-O-(p-tert-amylphenyl)thionophosphoric acid Octylamine salt of O-benzyl-S-isononylthiothionophosphoric acid Octylamine salt of O-cyclopentyl-O-heptadecylthiothionophosphoric acid Octylamine salt of O-oleyl-S-butyldithiothionophosphoric acid Octylamine salt of S-2-ethylhexyl-S-isooctyldithiothionophoshoric acid Octylamine salt of S-allyl-S-tridecyltrithiothionophosphoric acid. In addition to the octylamine salts or adducts given above for purposes of illustration, use can be made of the corresponding nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, hepta-decylamine, octadecylamine, cyclohexylamine, phenylamine, mesitylamine, oleylamine, cocoamine, soyamine, C₁₀₋₁₂ tertiary alkyl primary amines, and phenethylamine salts or adducts of the above and similar partially esterified acids of pentavalent phosphorus, including mixtures of any such compounds. Secondary hydrocarbyl amines and tertiary hydrocarbyl amines can also be used either alone or in combination with each other or in combination with primary amines. Thus any combination of primary, secondary and/or tertiary amines, whether monoamine or polyamine, can be used in forming the salts or adducts. Use of primary amines is preferred. It is perhaps worth noting that the above referred to partially esterified pentavalent acids of phosphorus have been named, for convenience, by use of the "thio-thiono" system of nomenclature. Such compounds can also be named by use of a "thioic" system of nomenclature. For example, S,S-dihydrocarbyltrithiothionophosphoric acid is also known as S,S-dihydrocarbylphosphorotetrathioic acid, (RS)₂P(S)(SH). Likewise, O,S-dihydrocarbylthiothionophosphoric acid is also known as O,S-dihydrocarbylphosphorodithioic acid, (RO)(RS)P(S)(OH); S,S-dihydrocarbyldithiophosphoric acid is also known as S,S-dihydrocarbylphosphorodithioic acid, (RS)₂P(O)(OH); and O,O-dihydrocarbylthionophosphoric acid is also known as O,O-dihydrocarbylphosphorothioic acid, (RO)₂P(S)(OH). Methods for the preparation of such amine salts are well known and reported in the literature. See for example, U.S. Pat. Nos. 2,063,629; 2,224,695; 2,447,288; 2,616,905; 3,984,448; 4,431,552; Pesin et al, Zhurnal Obshchei Khimii , Vol. 31, No. 8, pp. 2508-2515 (1961); and International Application Publication No. WO 87/07638. Component (iii) Compounds of this type are known in the art. For example European Patent Publication No. 20037, published December 10, 1980, describes their use as friction reducing additives in crankcase lubricating oils and in gasoline and diesel fuel. See also British Patent No. 1,111,837 published May 1, 1968 which suggests their use as ashless dispersants for engine oils and as rust inhibitors in a variety of lubricating oils, including engine oils. The synthesis method described in the European patent publication is deemed superior to that described in the British patent. As noted above, component (iii) can be a single compound or a mixture of two or more compounds of the formula where R₁ is an alkyl or alkenyl or polyunsaturated group having an average of 8 to 50, preferably an average of 14 to 30, and most preferably an average of 20 to 24 carbon atoms and each of R₂, R₃ and R₄ is independently, a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms. Most preferably each of R₂, R₃ and R₄ is a hydrogen atom. In the most preferred compounds R₁ is derived from an isomerized 1-olefin and thus is composed predominantly of at least one group (usually a plurality of groups) represented by the formula R₅R₆CH- wherein R₅ and R₆ are independently alkyl or alkenyl groups, which most preferably are linear or substantially linear. The total number of carbon atoms in R₅ and R₆ is of course one less than the number of carbon atoms in that particular R₁. Illustrative examples of these compounds are given below. In these examples (a) the numerals 3 and 4 designate the position(s) of the substituent(s) on the succinimide ring; (b) the secondary alkenyl substituents represent the predominant alkenyl groups formed when producing the compounds from the corresponding isomerized (predominantly internal) linear olefins by a process such as described in the above-referred to European patent publication; and (c) the secondary alkyl substituents represent the alkyl groups resulting from hydrogenolysis of the secondary alkenyl substituents: 3-octenylsuccinimide 3-octenyl-4-methylsuccinimide 3-octenyl-4,4-dimethylsuccinimide 3-octenyl-4-ethylsuccinimide 3-octenyl-4-ethyl-4-methylsuccinimide 3-octenyl-4-butylsuccinimide 3-octenyl-4-vinylsuccinimide 3-octenyl-4-allylsuccinimide 3-octenyl-4-butenylsuccinimide 3-sec-octenylsuccinimide 3-sec-octenyl-4-isopropylsuccinimide 3-octylsuccinimide 3-octyl-4-methylsuccinimide 3-sec-octylsuccinimide 3-sec-octyl-4-methylsuccinimide 3-sec-octyl-4-ethylsuccinimide 3-sec-octyl-4-propylsuccinimide 3-sec-octyl-4,4-dimethylsuccinimide 3-sec-octyl-4,4-diethylsuccinimide, and the like, and each of the corresponding compounds containing 9 through 50 carbon atoms in the alkyl or alkenyl substituent in the 3-position. Mixtures of two or more of any such compounds can also be used. An especially preferred succinimide for use as component (iii) is predominantly a mixture of C₂₀, C₂₂ and C₂₄ sec-alkenyl succinimides made from an isomerized 1-olefin mixture containing (wt %): C₁₈ max. 3 c₂₀ 45-55 C₂₂ 31-47 C₂₄ 4-15 C₂₆ max. 1 Component (iv) Component (iv) is composed of one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid or one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphorothioic acid, or a combination of one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid and one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphorothioic acid. Such compounds are represented by the general formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom. Thus when the compound has the formula: it is a fully-esterified hydrocarbyl ester of a phosphoric acid. On the other hand, when the compound has the formula: it is a fully-esterified hydrocarbyl ester of a phosphorothioic acid. In the foregoing formulas, the hydrocarbyl groups R₅, R₆ and R₇ can be any hydrocarbyl group, such as alkyl, cycloalkyl, aryl, cycloalkylalkyl, aralkyl, alkenyl, or cycloalkenyl. Such hydrocarbyl groups may each contain up to 50 or more carbon atoms, although ordinarily they will contain up to about 24 carbon atoms. The hydrocarbyl groups may be substituted by inert substituents in the sense that the substituents do not interfere with the functioning of the other components nor destroy the effectiveness of the compositions of this invention. For example, the hydrocarbyl groups of the phosphorus esters may include ether oxygen atoms, thioether sulfur atoms, nitrogen atoms, ester functionality, hydroxyl groups, sulfhydryl groups, and like substituents. Thus, the fully-esterified phosphate and phosphoricthioate esters used in the practice of this invention may include alkoxyalkyl, poly(alkoxy)alkyl, alkylthio-alkyl, aryloxyalkyl, dialkylaminoalkyl, diarylaminoalkyl, hydroxyalkyl, and like inert (innocuous) substituents. A preferred group of compounds for use as component (iv) are the O,O-dihydrocarbyl-S-hydrocarbyl phosphorothiothionates of the general formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group, especially where R₇ is an alicyclic hydrocarbyl group. Particularly preferred are the O,O-dialkyl-S-hydrocarbyl phosphorothiothionates wherein R₇ is an alicyclic group and R₅ and R₆ are alkyl groups each having up to 18 carbon atoms and most preferably up to 12 carbon atoms. Various phosphoric and phosphorothioic esters of the type depicted in formulas IV, V, VI, and VII above and methods for their preparation have been reported in the literature. See for example, U.S. Pat. Nos. 2,528,732, 2,561,773, 2,665,295, 2,767,206, 2,802,856, 3,023,209, and J. Org. Chem. , 1963 , 28, 1262-8. Exemplary compounds suitable for use as component (iv) include such fully-esterified phosphates and phosphorothioates as fusel oil phosphate, tricresyl phosphate, dibutyl phenyl phosphate, tri-2-ethylhexyl phosphate, triisodecyl phosphate, tri-lauryl phosphate, trioctylphosphorothiothionate, tridecylphosphorodithiothionate, trilaurylphosphorotrithiothionate, diethyl bicyclo(2.2.1)-hepten-2-yl phosphate, O,O-diethyl S-bicyclo-(2.2.1)-5-hepten-2-yl phosphorothiothionate, diethyl 7,7-dimethyl-bicyclo(2.2.1)-5-hepten-2-yl phosphate, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dimethyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dibutyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dibutyl ester with cis-endomethylene-tetrahydrophthalic acid dilauryl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-1-methyl-tetrahydrobenzoic acid butyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-1-methyl-tetrahydrobenzoic acid decyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-6-methyl-tetrahydrobenzoin acid ethyl ester, the product formed by reaction of dithiophosphoric acid-O,O-diethyl ester with 2,5-endomethylene-tetrahydrobenzyl alcohol, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with the Diels-Alder adduct of cyclopentadiene and allyl alcohol (2 mols : 1 mol), the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-tetrahydrophenyl acetate, the product formed by reaction of dithiophosphoric acid-O,O-dibutyl ester with the Diels-Alder adduct of cyclopentadiene and vinyl acetate (2 mols : 1 mol), the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with the bis-cyclopentadiene adduct of p-benzoquinone, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with the azodicarboxylic acid diethyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-dibutyl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-dioctyl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-dilauryl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-di-2-ethylhexyl ester with wax olefin, the product formed by reaction of dithiophosphoric acid-O,O-di-2-ethylhexyl ester with oleyl alcohol, the product formed by reaction of dithiophosphoric acid-O,O-di-2-ethylhexyl ester with linseed oil, the product formed by reaction of dithiophosphoric acid-O,O-diamyl ester with alpha pinene, the product formed by reaction of dithiophosphoric acid-O,O-diphenyl ester with alpha pinene, the product formed by reaction of dithiophosphoric acid-O,O-diamyl ester with allo-ocimene, the product formed by reaction of dithiophosphoric acid-O,O-dioctyl ester with dipentene, and the like. Component (v) As noted above, one preferred embodiment of this invention involves the additional presence in the compositions of one or more amine salts of one or more carboxylic acids, especially the amine salts of (a) one or more long chain monocarboxylic acids, or (b) one or more long chain polycarboxylic acids, or (c) a combination of at least one acid of (a) and at least one acid of (b). Generally speaking, these acids contain from 8 to 50 carbon atoms in the molecule and thus the salts are oil-soluble. A variety of amines can be used in forming such salts, including primary, secondary and tertiary amines, and the amines can be monoamines, or polyamines. Further, the amines may be cyclic or acyclic aliphatic amines, aromatic amines, heterocyclic amines, or amines containing various mixtures of acyclic and cyclic groups. Preferred amine salts include the alkyl amine salts of alkanoic acid and the alkyl amines salts of alkanedioic acids. The amine salts are formed by classical chemical reactions, namely, the reaction of an amine or mixture of amines, with the appropriate acid or mixture of acids. Accordingly, further discussion concerning methods for the preparation of such materials would be redundant. Among the amine salts of long-chain acids that may be used are the following: lauryl ammonium laurate (i.e. the lauryl amine salt of lauric acid), stearyl ammonium laurate, cyclohexyl ammonium laurate, octyl ammonium laurate, pyridine laurate, aniline laurate, lauryl ammonium stearate, stearyl ammonium stearate, cyclohexyl ammonium stearate, octylammonium stearate, pyridine stearate, aniline stearate, lauryl ammonium octanoate, stearyl ammonium octanoate, cyclohexyl ammonium octanoate, octyl ammonium octanoate, pyridine octanoate, aniline octanoate, nonyl ammonium laurate, nonyl ammonium stearate, nonyl ammonium octanoate, lauryl ammonium nonanoate, stearyl ammonium nonanoate, cyclohexyl ammonium nonanoate, octyl ammonium nonanoate, pyridine nonanoate, aniline nonanoate, nonyl ammonium nonanoate, lauryl ammonium decanoate, stearyl ammonium decanoate, cyclohexyl ammonium decanoate, octyl ammonium deconoate, pyridine decanoate, aniline decanoate, decyl ammonium laurate, decyl ammonium stearate, decyl ammonium octanoate, decyl ammonium nonanoate, decyl ammonium decanoate, bis octyl amine salt of suberic acid, bis cyclohexyl amine salt of suberic acid, bis lauryl amine salt of suberic acid, bis stearyl amine salt of suberic acid, bis octyl amine salt of sebacic acid, bis cyclohexyl amine salt of sebacic acid, bis lauryl amine salt of sebacic acid, bis stearyl amine salt of sebacic acid, the tert-dodecyl and tert-tetradecyl primary amine salts of octanoic acid, the tert-decyl and tert-dodecyl primary amine salts of octanoic acid, the tert-dodecyl and tert-tetradecyl primary amine salts of lauric acid, the tert-decyl and tert-dodecyl primary amine salts of lauric acid, the tert-dodecyl and tert-tetradecyl primary amine salts of stearic acid, the tert-decyl and tert-dodecyl primary amine salts of stearic acid, the hexyl amine salt of C₂₄-dicarboxylic acid, the octyl amine salt of C₂₈-dicarboxylic acid, the octyl amine salt of C₃₀-dicarboxylic acid, the decyl amine salt of C₃₀-dicarboxylic acid, the octyl amine salt of C₃₂-dicarboxylic acid, the bis lauryldimethyl amine salt of traumatic acid, diethyl ammonium laurate, dioctyl ammonium laurate, dicyclohexyl ammonium laurate, diethyl ammonium octanoate, dioctyl ammonium octanoate, dicyclohexyl ammonium octanoate, diethyl ammonium stearate, dioctyl ammonium stearate, diethyl ammonium stearate, dibutyl ammonium stearate, dicyclopentyl ammonium stearate, dipropyl ammonium benzoate, didecyl ammonium benzoate, dimethylcyclohexyl ammonium benzoate, triethyl ammonium laurate, triethyl ammonium octanoate, triethyl ammonium stearate, triethyl ammonium benzoate, trioctyl ammonium laurate, trioctyl ammonium octanoate, trioctyl ammonium stearate, trioctyl ammonium benzoate, and the like. It will be understood of course that the amine salt of the monocarboxylic and/or polycarboxylic acid used should be sufficiently soluble in the base oil used as to provide homogeneous solution at the concentration employed. Among the preferred amine salts for use in practice of this invention are the primary amine salts of long chain monocarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH₂; the secondary amine salts of long chain monocarboxylic acids in which the amine thereof is a dialkyl monoamine, R₂NH; the tertiary amine salts of long chain monocarboxylic acids in which the amine thereof is a trialkyl monoamine, R₃N; the bis primary amine salts of long chain dicarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH₂; the bis secondary amine salts of long chain dicarboxylic acids in which the amine thereof is a dialkyl monoamine, R₂NH; the bis tertiary amine salts of long chain dicarboxylic acids in which the amine thereof is a trialkyl monoamine, R₃N; and mixtures thereof. In the foregoing formulae, R is an alkyl group which contains up to 30 or more carbon atoms, and preferably from 6 to 24 carbon atoms. Component (vi) Another type of component which is preferably utilized in the compositions of this invention is comprised of the nitrogen-containing ashless dispersants. Thus, in accordance with a preferred embodiment of this invention, the composition additionally contains at least one nitrogen-containing ashless dispersant such as a hydrocarbyl substituted succinimide, a hydrocarbyl substituted succinic acid, a hydrocarbyl substituted succinamide, a hydrocarbyl substituted succinic ester/amide, a long-chain hydrocarbyl amine, a Mannich-type ashless dispersant, or the like. Such materials are well known in the art. Thus for a description of typical hydrocarbyl succinimides, which include post-treated hydrocarbyl succinimides, reference may be had, for example, to the following U.S. Patents: 3,018,247; 3,018,250; 3,018,291; 3,087,936; 3,172,892; 3,184,411; 3,184,474; 3,185,645; 3,185,704; 3,194,812; 3,194,814; 3,200,107; 3,202,678; 3,215,707; 3,219,666; 3,231,587; 3,254,025; 3,256,185; 3,272,746; 3,272,746; 3,278,550; 3,280,034; 3,281,428; 3,282,955; 3,284,410; 3,287,271; 3,311,558; 3,312,619; 3,331,776; 3,338,832; 3,341,542; 3,344,069; 3,346,354; 3,347,645; 3,359,204; 3,361,673; 3,366,569; 3,367,943; 3,369,021; 3,373,111; 3,381,022; 3,390,086; 3,399,141; 3,401,118; 3,458,530; 3,470,098; 3,502,677; 3,511,780; 3,513,093; 3,541,012; 3,551,466; 3,558,473; 3,573,205; 3,576,743; 3,578,422; 3,652,616; 3,658,494; 3,658,495; 3,718,663; 3,749,695; 3,865,740; 3,865,813; 3,912,764; 3,954,639; 4,110,349; 4,234,435; 4,338,205; 4,374,033; 4,401,581; 4,410,437; 4,428,849; 4,548,724; 4,554,086; 4,608,185; 4,612,132; 4,614,603; 4,615,826; 4,645,515; 4,710,201; 4,713,191; 4,746,446; 4,747,963; 4,747,964; 4,747,965; and 4,857,214. See also British 1,085,903 and British 1,162,436. Mixed ester-amides of hydrocarbyl substituted succinic acids using alkanols, amines and/or amino-alkanols are described, for example, in U.S. Pat. Nos. 3,576,743 and 4,234,435. Another type of ashless dispersant which can be used in the practice of this invention comprises the hydrocarbyl substituted succinic acid esters and the hydrocarbyl substituted succinic acid salts. Such well-known additives and their preparation are described in the literature such as for example in U.S. Pat. No. 4,234,435 and references cited therein. Amine dispersants and methods for their production from high molecular weight aliphatic or alicyclic halides and amines are described for example, in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; and 3,565,804. For a description of Mannich-type ashless dispersants which can be used in the practice of this invention, see for example the following U.S. Patents: 3,368,972; 3,413,347; 3,442,808; 3,448,047; 3,539,633; 3,591,598; 3,600,372; 3,634,515; 3,697,574; 3,703,536; 3,704,308; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; and 3,803,039. The preferred ashless dispersants are hydrocarbyl succinimides in which the hydrocarbyl substituent is a hydrogenated or unhydrogenated polyolefin group and preferably a polyisobutene group having a number average molecular weight (as measured by gel permeation chromatography) of from 250 to 10,000, and more preferably from 500 to 5,000, and most preferably from 750 to 2,500. The ashless dispersant is most preferably an alkenyl succinimide such as is available commercially from Ethyl Petroleum Additives, Inc. and Ethyl Petroleum Additives, Ltd. as HITEC® 644 and HITEC® 646 additives. The ashless dispersants which can be used in the compositions of this invention also include ashless dispersants of the types described above which have been subjected to post-treatment with a suitable post-treating reagent. In preparing a post-treated ashless dispersant, any of a wide variety of post-treating agents can be used. Such post-treating agents include, for example, boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulphide, hydrogen sulphide, sulfur, sulfur chloride, alkenyl cyanides, carboxylic acid acylating agents, aldehyde, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulphides, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulphides, formaldehyde or formaldehyde producing compounds plus phenols, sulfur plus phenols, and many others. Preferred post-treating agents and procedures involve use of phosphorus-containing post-treating agents or boron-containing post-treating agents. The phosphorus-containing post-treating agents comprise organic compounds capable of reacting with the dispersant in order to introduce phosphorus or phosphorus-containing moieties into the dispersant. Thus use can be made of such organic phosphorus compounds as monohydrocarbyl phosphites, dihydrocarbyl phosphites, trihydrocarbyl phosphites, monohydrocarbyl phosphates, dihydrocarbyl phosphates, trihydrocarbyl phosphates, the hydrocarbyl pyrophosphates, and their partial or total sulfur analogs wherein the hydrocarbyl group(s) contain up to about 30 carbon atoms each. The boron-containing post-treating agents comprise both inorganic and organic compounds capable of reacting with the dispersant in order to introduce boron or boron-containing moieties into the dispersant. Accordingly, use can be made of such inorganic boron compounds as the boron acids, and the boron oxides, including their hydrates. Typical organic boron compounds include esters of boron acids, such as the orthoborate esters, metaborate esters, biborate esters, pyroboric acid esters, and the like. It is particularly preferred to utilize an ashless dispersant, most especially a hydrocarbyl-substituted succinimide dispersant, that contains only carbon, hydrogen, nitrogen, and optionally oxygen and/or sulfur atoms in its chemical structure. Such compounds produce little or no adverse deposits on critical mechanical parts during actual service. Diluents The additive concentrates of this invention preferably contain a suitable diluent, most preferably an oleaginous diluent of suitable viscosity. Such diluent can be derived from natural or synthetic sources. Among the mineral (hydrocarbonaceous) oils are paraffin base, naphthenic base, asphaltic base and mixed base oils. Typical synthetic base oils include polyolefin oils (especially hydrogenated α-olefin oligomers), alkylated aromatics, polyalkylene oxides, aromatic ethers, and carboxylate esters (especially diester oils), among others. Blends of natural and synthetic oils can also be used. The preferred diluents are the light hydrocarbon base oils, both natural or synthetic. Generally the diluent oil will have a viscosity in the range of 13 to 35 centistokes at 40°C, and preferably in the range of 18.5 to 21.5 centistokes at 40°C. A 100 neutral mineral oil with a viscosity of about 19 centistokes at 40°C with a specific gravity (ASTM D1298) in the range of 0.855 or 0.893 (most preferably about 0.879) at 15.6°C (60°F) and an ASTM color (D1500) of 2 maximum is particularly preferred for this use. Gear oil base stocks The gear oils in which the compositions of this invention are employed can be based on natural or synthetic oils, or blends thereof, provided the lubricant has a suitable viscosity for use in gear oil applications. Thus the base oils will normally have a viscosity in the range of SAE 50 to SAE 250, and more usually will range form SAE 70W to SAE 140. Suitable automotive gear oils also include cross-grades such as 75W-140, 80W-90, 85W-140, 85W-90, and the like. The base oils for such use are generally mineral oil base stocks such as for example conventional and solvent-refined paraffinic neutrals and bright stocks, hydrotreated paraffinic neutrals and bright stocks, naphthenic oils, or cylinder oils, including straight run and blended oils. Synthetic base stocks can also be used in the practice of this invention, such as for example poly-α-olefin oils (PAO), alkylated aromatics, polybutenes, diesters, polyol esters, polyglycols, or polyphenyl ethers, and blends thereof. Typical of such oils are blends of poly-alpha-olefins with synthetic diesters in weight proportions (PAO:ester) ranging from 95:5 to 50:50, typically 75:25. Proportions In forming the gear oils of this invention, the lubricant base stocks will contain components (i), (ii), (iii) and (iv), and optionally but preferably one or more of components (v) and (vi), in the following concnetrations (weight percentages of active ingredients): Component Preferred Range More Preferred Range Most Preferred Range (i) 1 - 5 1.5 - 4.5 2 - 4 (ii) 0.1 - 3 0.2 - 2 0.3 - 1 (iii) 0.05 - 4 0.1 - 2 0.2 - 1 (iv) 0.2 - 5 0.5 -3 0.75 - 1.5 (v) 0.001 - 2 0.01 - 2 0.2 - 1 (vi) 0.1 - 4 0.3 - 2 0.5 - 1 In the additive concentrates containing a diluent such as an oleaginous liquid, the total content of the active ingredients of this invention (i.e., components (i), (ii), (iii) and (iv) and preferably also one or more of (v) and (vi), falls within the range of 1 to 13%, preferably 1.5 to 10%, and most preferably 2 to 9% based on the total weight of the concentrate (including other ancillary components, if used). The proportions of components (i), (ii), (iii) and (iv) and preferably also one or more of components (v) and (vi) in the additive concentrates of this invention are as follows: Component Preferred Range More Preferred Range Most Preferred Range (i) 20 - 80 30 - 70 35 - 65 (ii) 1 - 15 3 - 12 5 - 10 (iii) 1 - 20 3 - 15 5 - 10 (iv) 5 - 30 5 - 25 10 - 25 (v) 0 - 12 0.4 - 5 0.5 - 2 (vi) 0 - 50 3 - 12 5 - 10 Other components, such as described below, can also be included in such additive concentrates. Other components The gear oils and gear oil additive concentrates of this invention can contain various other conventional additives to partake of their attendant functions. These include, for example, the following materials: Defoamers - Illustrative materials of this type include silicone oils of suitable viscosity, glycerol monostearate, polyglycol palmitate, trialkyl monothiophosphates, esters of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, glycerol dioleate, and the like. Defoamers are generally employed at concentrations of up to about 1% in the additive concentrate. Demulsifiers - Typical additives which may be employed as demulsifiers in gear oils include alkyl benzene sulfonates, polyethylene oxides, polypropylene oxides, esters of oil soluble acids, and the like. Such additives are generally employed at concentration of up to about 3% in the additive concentrate. Sulfur scavengers - This class of additives includes such materials as thiadiazoles, triazoles, and in general, compounds containing moieties reactive to free sulfur under elevated temperature conditions. See for example U.S. Pat. Nos. 3,663,561 and 4,097,387. Concentrations of up to about 3% in the concentrate are typical. Antioxidants - Ordinarily, antioxidants that may be employed in gear oil formulations include phenolic compounds, amines, phosphites, and the like. Amounts of up to about 5% in the concentrate are generally sufficient. Other commonly used additives or components include anti-rust agents or rust inhibitors, corrosion inhibitors, detergents, dyes, metal deactivators, pour point depressants, and diluents. As noted above, the preferred compositions of this inventional are essentially devoid of metal-containing components. For the purposes of this invention, boron is not considered to be a metal and thus the compositions of this invention may contain boron-containing components. Examples 1-4 illustrate typical additive concentrates of this invention. In these examples, "pbw" represents parts by weight of the specific ingredient, which in the case of the succinimides, is the amount of active ingredient. EXAMPLE 1 Di-tert-nonyl trisulfide 600 pbw Palmitic amine salt of O,O-di-2-ethylhexyl phosphoric acid 75 pbw Polypropenylsuccinimide 120 pbw Trilauryl phosphorothioate 235 pbw 100 Neutral Oil (19 centistokes at 40°C) 300 pbw EXAMPLE 2 Dibenzyl disulfide 700 pbw Stearyl amine salt of 2-ethylhexyl acid phosphate 100 pbw Isomerized eicosenyl succinimide 110 pbw Trihydrocarbyl phosphorodithioate 180 pbw Polyisobutenyl succinimide of tetraethylene pentamine 100 pbw 100 Neutral Oil (19 centistokes at 40°C) 300 pbw EXAMPLE 3 Sulfurized isobutylene 500 pbw C₁₀ and C₁₂ dialkyl amine salts of octyl phosphorotetrathioic acid 150 pbw Isomerized C₁₆, C₁₈, C₂₀ alkenylsuccinimide 125 pbw Boronated polyisobutenyl succinimide of tetraethylene pentamine 100 pbw Octyl and decyl amine salts of octanoic acid 30 pbw O,O-dialkyl-S-dicyclopentadienyl phosphorodithioate 300 pbw 100 Neutral Oil (19 centistokes at 40°C) 270 pbw EXAMPLE 4 Sulfurized isobutylene 460 pbw Oleyl amine salts of O,O-dibutyl phosphorodithioate 80 pbw C₂₀, C₂₂, C₂₄ Alkenylsuccinimide 100 pbw Polyisobutenyl succinimide of tetraethylene pentamine 225 pbw O,O-dialkyl-S-dicyclopentadienyl phosphorodithioate 300 pbw Myristyl amine salt of lauric acid 25 pbw 100 Neutral Oil (19 centistokes at 40°C) 290 pbw Examples 5-13 illustrate gear oil compositions of this invention. The base oils used in these examples are mineral oil base stocks, synthetic base stocks and suitable combinations of mineral oil and synthetic base oils. Such base oils may contain a viscosity index improver if desired. The percentages given in these examples are by weight and are based on the total weight of the base oil plus additives. For example, components totaling 2.15% are present in a gear oil composition containing 97.85% of the base oil. The components identified in these examples are preferably added in the form of an additive concentrate of this invention. They can, however, be blended into the base oil separately or in various sub-combinations. EXAMPLE 5 Automotive gear oils with SAE straight grades of 75 or lower and automotive gear oils with SAE cross grades having a light viscosity end of 75W or lower are blended to contain the following components: Sulfurized lard oil 4.95% Dodecyl amine salt of diaryl phosphorotetrathioate 0.75% Polyisobutenyl succinimide 0.75% Tricresyl phosphate 1.50% 7.95 % EXAMPLE 6 Example 5 is repeated except that the base gear oils are of SAE grades heavier than 75 and the total of the components (used in the same relative proportions) is 5.3%. EXAMPLE 7 Example 5 is repeated except that the oils are designed for industrial oil usage and thus the base oil has a ISO viscosity grade in the range of 68 to 460. In this case the total of the components (used in the same relative proportions) is 2.1%. EXAMPLE 8 Automotive gear oils with SAE straight grades of 75 or lower and automotive gear oils with SAE cross grades having a light viscosity end of 75W or lower are blended to contain the following components: Sulfurized isobutylene 3.41% Oleyl amine salts of dibutyl phosphorothioate 0.60% C₂₀, C₂₂, C₂₄ Alkenylsuccinimide 0.75% Oleylamine salts of a 50-50 mixture of octanoic acid and dimerized linoleic acid 0.24% Polyisobutenylsuccinimide of tetraethylene pentamine 1.20% O,O-dialkyldicyclopentadienyl phosphorodithioate 1.62% 7.82% EXAMPLE 9 Example 8 is repeated except that the base gear oils are of SAE grades heavier than 75 and the total of the components (used in the same relative proportions) is 5.24%. EXAMPLE 10 Example 8 is repeated except that the oils are designed for industrial oil usage and thus the base oil has a ISO viscosity grade in the range of 68 to 460. In this case the total of the components (used in the same relative proportions) is 2.06%. EXAMPLES 11-13 Examples 8-10 are repeated except that the polyisobutenyl succinimide is boronated to a boron content of approximately 1.3%. The effectiveness of the compositions of this invention in alleviating the problem of noise and chatter in limited slip differentials was illustrated by tests conducted in accordance with the GM limited slip axle chatter test (R-4A1-4). In the version of the test employed, the vehicle used was a 1986 Buick Grand National having a 3.8 liter turbo-charged V-6 engine with single port fuel injection. The vehicle was equipped with an automatic transmission, power steering and brakes, and a clutch pack "plate" limited slip differential. Prior to each test the rear axle was dissembled to allow replacement of the limited slip clutch packs, plates and springs. The entire assembly was washed with Stoddard solvent and air-dried to remove traces of any previous lubricant. The axle was assembled and lubricated with the test lubricant and a thermocouple was installed into the axle assembly to allow recording of lubricant temperature. The unit was bias checked, then run-in with equal size rear tires at 64 to 80 kph (40 to 50 mph) for 80 km (fifty miles). After the run-in, tires of different diameters were installed on the rear of the vehicle to obtain the specified differential rate between right and left wheel, the larger diameter tire being installed on the right rear position. At the recommendation of General Motors, E78 x 15 and L78 x 15 tires were used, resulting in approximately 5 to 5.6 revolutions per km (eight to nine revolutions per mile) differential rate. The test consisted of mileage accumulation at 88 to 96 kph (55 to 60 mph) with rear axle lubricant temperature between 138° and 149°C (280°F and 300°F). The axle was insulated and the speed was varied slightly to maintain temperature within limits. Chatter checks were performed at approximately 160 km (100-mile) intervals and torque bias checks were performed each 1600 km (thousand miles) and at test completion. The torque bias check consisted of placing one rear wheel on a low friction surface and a 2 x 4 block tightly in front of a front wheel. The vehicle was slowly accelerated to pull over the block. The low friction wheel should not spin freely. The chatter check consisted of the car being driven through eight (8) figure "8" lock to lock turns at 8 to 13 kph (5 to 8 mph). A thirty-second stop was made before each check and after completing each circle. Any chatter, roughness or unusual noise was noted. Four such tests were conducted. In one test, a "passing" reference gear oil (a GM factory fill for limited slip differentials) was used. In a second test, a "failing" reference oil (a GL-5 non-limited slip gear lubricant) was used. The other two tests involve use of an SAE 80W-90 gear oil base stock containing in both cases 5.5% of a commercially available fully formulated gear oil additive containing 23% by weight of sulfur, 2.2% by weight of phosphorus, and 0.4% by weight of nitrogen. In one test this gear oil was used as is. In the other test, the gear oil contained a formulation comparable to that of Example 12. The test results were as follows: Test No. Composition Results 1 "Passing" reference Pass after 9656 km (6000 miles) 2 "Failing" reference Fail after 2736 km (1700 miles) 3 Commercial Product Fail after 4023 km (2500 miles) 4 This Invention Pass after 9656 km (6000 miles)

Claims: A gear oil additive concentrate which comprises: (i) at least one oil-soluble sulfur-containing extreme pressure or antiwear agent; (ii) at least one oil-soluble amine salt of a partial ester of an acid of phosphorus; (iii) at least one oil-soluble succinimide of the formula wherein R₁ is an alkyl or alkenyl group having an average of 8 to 50 carbon atoms, and each of R₂, R₃ and R₄ is, independently, a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms; and (iv) at least one oil-soluble fully esterified hydrocarbyl ester of phosphoric acid or phosphorothioic acid of the formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom. A composition as claimed in claim 1 wherein the said ester (iv) is of the formula: wherein each of R₅, R₆ and R₇ is alkyl, cycloalkyl, aryl, cycloalkylalkyl, aralkyl, alkenyl, or cycloalkenyl of up to 24 carbon atoms. A composition as claimed in claim 1 or 2 wherein, in the oil-soluble succinimide (iii), each of R₂, R₃ and R₄ is a hydrogen atom, and R₁ is composed of a plurality of groups represented by the formula R₅R₆CH- where R₅ and R₆ are independently alkyl or alkenyl groups and the total number of carbon atoms in R₁ is 14 to 30. A composition as claimed in claim 2 or 3 also containing at least one additive selected from amine salts of carboxylic acids, and nitrogen-containing ashless dispersants. A composition as claimed in claim 4 containing both at least one amine salt of a carboxylic acid and at least one nitrogen-containing ashless dispersant. A gear oil additive concentrate which comprises: (i) at least one oil-soluble sulfur-containing extreme pressure or antiwear agent; (ii) at least one oil-soluble amine salt of a partial ester of an acid of phosphorus; (iii) at least one oil-soluble succinimide of the formula wherein R₁ is an alkyl or alkenyl group having an average of 8 to 50 carbon atoms, and each of R₂, R₃ and R₄ is, independently, a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms; and (iv) at least one oil-soluble fully esterified hydrocarbyl ester of phosphoric acid or phosphorothione acid of the formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom; said gear oil additive concentrate being essentially devoid of any metal-containing additive component. A composition as claimed in claim 6 wherein the said ester (iv) is of the formula: wherein each of R₅, R₆ and R₇ is alkyl, cycloalkyl, aryl, cycloalkylalkyl, aralkyl, alkenyl, or cycloalkenyl of up to 24 carbon atoms. A composition as claimed in claim 6 or 7 wherein, in the oil-soluble succinimide (iii), each of R₂, R₃ and R₄ is a hydrogen atom, and R₁ is composed of a plurality of groups represented by the formula R₅R₆CH- where R₅ and R₆ are independently alkyl or alkenyl groups and the total number of carbon atoms in R₁ is 14 to 30. A composition as claimed in claim 6, 7 or 8 also containing at least one additive selected from oil-soluble amine salts of carboxylic acids, and oil-soluble nitrogen-containing ashless dispersants. A composition as claimed in claim 7 containing both at least one oil-soluble amine salt of a carboxylic acid, and at least one oil-soluble nitrogen-containing ashless dispersant. A gear oil composition which comprises a major proportion of at least one oil of lubricating viscosity and a minor effective amount of: (i) at least one oil-soluble sulfur-containing extreme pressure or antiwear agent; (ii) at least one oil-soluble amine salt of a partial ester of an acid of phosphorus; (iii) at least one oil-soluble succinimide of the formula wherein R₁ is an alkyl or alkenyl group having an average of 8 to 50 carbon atoms, and each of R₂, R₃ and R₄ is, independently, a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms, and (iv) at least one oil-soluble fully esterified hydrocarbyl ester of phosphoric acid or phosphorothioic acid of the formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom. A composition as claimed in claim 11 wherein the said ester (iv) is of the formula: wherein each of R₅, R₆ and R₇ is alkyl, cycloalkyl, aryl, cycloalkylalkyl, aralkyl, alkenyl, or cycloalkenyl of up to 24 carbon atoms. A composition as claimed in claim 11 or 12 wherein, in the oil-soluble succinimide (iii), each of R₂, R₃ and R₄ is a hydrogen atom, and R₁ is composed of a plurality of groups represented by the formula R₅R₆CH- where R₅ and R₆ are independently alkyl or alkenyl groups and the total number of carbon atoms in R₁ is 14 to 30. A composition as claimed in claim 11, 12 or 13 additionally containing at least one oil-soluble amine salt of a carboxylic acid, and at least one oil-soluble nitrogen-containing ashless dispersant. A gear oil composition which comprises a major proportion of at least one oil of lubricating viscosity and a minor effective amount of: (i) at least one oil-soluble sulfur-containing extreme pressure or antiwear agent; (ii) at least one oil-soluble amine salt of a partial ester of an acid of phosphorus; (iii) at least one oil-soluble succinimide of the formula wherein R₁ is an alkyl or alkenyl group having an average of 8 to 50 carbon atoms, and each of R₂, R₃ and R₄ is, independently, a hydrogen atom or an alkyl or alkenyl group having an average of up to about 4 carbon atoms; and (iv) at least one oil-soluble fully esterified hydrocarbyl ester of phosphoric acid or phosphorothioic acid of the formula: wherein each of R₅, R₆ and R₇ is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom; said gear oil composition being essentially devoid of any metal-containing additive component. A composition as claimed in claim 15 wherein, in the oil-soluble succinimide (iii), each of R₂, R₃ and R₄ is a hydrogen atom, and R₁ is composed of a plurality of groups represented by the formula R₅R₆CH- where R₅ and R₆ are independently alkyl or alkenyl groups and the total number of carbon atoms in R₁ is 14 to 30. A composition as claimed in claim 15 or 16 additionally containing at least one oil-soluble amine salt of a carboxylic acid, and at least one oil-soluble nitrogen-containing ashless dispersant.

Inventors: CAMPBELL DONALD GALE, CONARY GREGORY STEVEN, NORMAN STEPHEN, CAMPBELL, DONALD GALE, CONARY, GREGORY STEVEN, NORMAN, STEPHEN
Applicants: ETHYL PETROLEUM ADDITIVES INC, ETHYL PETROLEUM ADDITIVES, INC.
Application year: 1991
Main classification: C10M141
IPC codes: C10N40, C10N30, C10M141