JPH11513720A - Transmission Fluid with Improved Shift Durability - Google Patents

Abstract

  (57) [Summary] Shift durability of transmission fluids, such as manual transmission fluids, is improved by the combination of amine phosphate and additives incorporating a neutral or acidic friction modifier.

Description

DETAILED DESCRIPTION OF THE INVENTION               Transmission Fluid with Improved Shift DurabilityBackground of the Invention   The present invention relates to transmissions, such as transmission fluids, in particular manual transmission fluids (MTF). Compositions and methods for improving the shift durability of device fluids, and more particularly MTF For improved synchromesh durability.   The usual goal of a car manufacturer is to have durability over the life of the car, To produce a car that works reliably. In the case of MTF, until the life of the car Not only should the transmission fail during the period of The shift characteristics must not change appreciably over time. Of manual transmission Since the shift characteristics are highly dependent on the friction characteristics, the MTF is time-dependent and therefore It needs to have very stable friction performance with mileage. NTF performance This aspect is known as friction performance. Today, many car manufacturers are now Required for shift durability as fluid is not drained and not replaced regularly There is a shift to a “fill-for-life” fluid.   European Patent 237,804 describes "clashing" (for high speed gear shifts). Problem identified) and "sticking" (slow gear shift issues) The problem of synchromesh gearshift, identified by the To 5 parts of sulfurized oil or sulfurized ester, 0.1 to 5 parts of phosphite, 0.2 to 5 parts Base oil containing the essential components of zinc dithiophosphate and 2 to 5 parts of a metallic detergent. It is intended to solve by providing. However, this publication is an improvement The shift endurance problem is not addressed.   The inventors of the present application have proposed a combination of an amine phosphate and a neutral and / or acidic friction modifier. Found to impart significant shift durability to MTF.Summary of the Invention   The present invention (1) Large amount of lubricating oil and (2) (a) amine phosphate and   (b) Neutral or acidic friction modifier   An effective amount of an additive formulation for improving shift durability, comprising: Gear fluid composition for improving shift durability of gear fluid containing the same And methods.Detailed description of the invention   The present invention describes compositions and methods for improving shift durability of transmission fluids. I do. Although the advantages of the present invention have been illustrated in manual transmissions, they have The points are fluid for automatic transmission, gear oil, hydraulic oil, heavy hydraulic oil, industrial oil, power Other such as alling fluid, pump oil, tractor fluid, universal tractor fluid etc It can be equally applied to transmission fluids of the type. These transmission fluids are It can be compounded with various performance additives and can be compounded in various base oils.Lubricant   Useful lubricating oils in the present invention include natural lubricating oils, synthetic lubricating oils and mixtures thereof. Derived from Generally, natural and synthetic lubricating oils, respectively, are typical About 2 to about 8mm at 100 ℃ for use^TwoPer second (cSt). It's important, about 1 to about 40mm at 100 ℃^TwoPer second (cSt).   Natural lubricating oils include animal oils, vegetable oils (eg, castor oil and lard oil), petroleum oil , Mineral oils, and oils derived from coal or shale. Favorable lubrication The oil is a mineral oil.   Suitable mineral oils include normal mineral oil base stocks included. This mineral oil basestock may have naphthenic or Paraffinic. Acid, alkali and clay or aluminum chloride Purified by conventional methods using other agents such as pheno Solvents such as toluene, sulfur dioxide, furfural, dichlorodiethyl ether, etc. It can be an extraction oil produced by the solvent extraction used. They are hydrotreated Or hydrorefined and dewaxed by cooling or catalytic dewaxing methods; or Hydrogen can be cracked. Mineral oil can be produced from natural crude sources or isomerized waxes. Or other purification steps.   Typically, mineral oil is 2.0-8.0 mm at 100 ° C.^TwoPer second (cSt) kinematic viscosity Have. Preferred mineral oils are 2-6 mm at 100 ° C.^TwoPer second (cSt) kinematic viscosity With, most preferably 3-5 mm at 100 ° C^TwoHas a kinematic viscosity of / cSt Things.   Synthetic lubricants include oligomerized, polymerized and interpolymerized Olefins [eg, polybutylenes, polypropylenes, propylene Polymer, isobutylene copolymer, chlorinated polylactenes, poly (1-hexene ), Poly (1-octene) s, poly (1-decene) s and mixtures thereof] Hydrocarbon oils and halo-substituted hydrocarbon oils; alkylbenzenes [eg, dodeci Benzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethyl Xyl) benzene and the like]; polyphenyls [eg, biphenyls, terphenyl , Alkylated polyphenyls, etc .; and alkylated diphenyl ethers, Alkylated diphenyl sulfides and their derivatives, analogs and homologues included. Preferred oils of these types of synthetic oils are oligomers of α-olefins And especially oligomers of 1-decene.   Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copoly And those whose terminal hydroxy groups have been modified by esterification, etherification, etc. These derivatives are included. Examples of this type of synthetic oil are ethylene oxide or pro Polyoxyalkylene polymers produced by the polymerization of pyrene oxide; The alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., A methyl-polyisopropylene glycol alcohol having an average molecular weight of 1,000, Diphenyl ether of polypropylene glycol having a molecular weight of 1,000 to 1,500 And their mono- and poly-carboxylic acid esters (eg, tetraethyl Acetic acid ester of lenglycol, mixed C_Three-C₈Fatty acid ester and C₁₂Oh Oxo acid diester).   Other suitable types of synthetic lubricating oils include dicarboxylic acids (eg, phthalic acid, succinic Acids, alkyl succinic and alkenyl succinic acids, maleic acid, azelaic acid, Veric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid , Alkylmalonic acid, alkenylmalonic acid, etc. Tyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl Alcohol, ethylene glycol, diethylene glycol monoethers, pro Esters with pyrene glycol). Specific examples of those esters Includes dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl Rufumarate, dioctyl sebacate, diisooctyl azelate, diisodeci Luazelate, dioctyl phthalate, didecyl phthalate, dieicosyl seba Kate, 2-ethylhexyl diester of linoleic acid dimer, 1 mole of sebacine Reaction of acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid And the like. From this kind of synthetic oil A preferred type of oil is C_FourOr C₁₂It is an adipate of alcohol.   Esters useful as synthetic lubricating oils include C_FiveOr C₁₂Monocarboxylic acids and , Neopentyl glycol, trimethylolpropane, pentaerythritol, Polyols such as dipentaerythritol, tripentaerythritol and the like; Includes esters made from polyol ethers.   Silicon-based oils (polyalkyl-, polyaryl-, polyalkoxy- or polyary Loxy-siloxane oils and silicate oils) are other useful classes of synthetic Make up the lubricating oil. These oils include tetraethyl silicate, tetraisopro Pill silicate, tetra (2-ethylhexyl) silicate, tetra (4-methyl-2 -Ethylhexyl) silicate, tetra (p-tert-butylphenyl) silicate , Hexa (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxane And poly (methylphenyl) siloxane. Other synthetic lubricants include: Liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctylpho Sulfate and diethyl ester of decyl phosphoric acid), tetrahydrofura of polymer And poly-α-olefins.   Lubricating oils can be derived from refined, rerefined oils, or mixtures thereof. . Unrefined oils can be natural or synthetic (eg, coal, shale, or tar) From sand bitumen) without further purification or treatment. Non-refined Examples of oils include shale oil obtained directly by retorting by distillation, and distillation. R Includes petroleum obtained directly or ester oil obtained directly from the esterification process. Are used without further processing. Refined oils have one or more properties modified. Same as unrefined oil except it has been treated in one or more refining steps to improve It is. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or Includes base extraction, filtration and percolation, all of which are within the skill of the art. Is known to. Rerefined oil is used to convert used oil to refined oil. It is obtained by performing the treatment in the same step as described above. Those rerefined oils also Known as raw oil or reprocessed oil, often used for removal of additives and oil cracking Further processing by techniques for product removal.   Lubricating oils are mixtures of natural and synthetic lubricating oils (ie, partially synthetic oils). In some cases, the oil is typically 1-80% by weight, preferably about 10-75% by weight. %, Most preferably about 10 to 50% by weight of a synthetic lubricating oil. Partially synthetic oil The choice of components can vary widely, but a particularly useful combination is mineral oil and poly-α- Refin (PAO), especially composed of 1-decene oligomers.Amine phosphate   The amine phosphates useful in the present invention are acidic phosphorus containing intermediates and the neutralization of amines Or partially neutralized product. The acidic intermediate is preferably a phosphorothioic acid Hydroxy-substituted triesters and the group consisting of phosphoric acid, phosphorus oxides and phosphorus halides It is produced from the selected inorganic phosphorus active substance.   The hydroxy-substituted triester of phosphorothioic acid has the structural formula: Wherein R is a substantially hydrocarbon group and a hydroxy-substituted substantially hydrocarbon Selected from the group consisting of groups wherein at least one of the R groups is substituted with a hydroxy group X is selected from the group consisting of sulfur and oxygen; And one X group is sulfur) Is mainly contained. Substantially hydrocarbon groups include aryl , Such as alkyl, aralkyl, alkaryl and cycloalkyl groups Aromatic, aliphatic and alicyclic groups. Such groups include chloro, bromo, Such as iodo, alkoxy, aryloxy, nitro, keto or aldehyde groups It has a polar substituent. In most cases, more than one It should not have such polar groups.   Particular examples of substantially hydrocarbon groups are methyl, ethyl, isopropyl, sec-butyl. , Isobutyl, n-pentyl, dodecyl, polyisobutene groups (molecular weight of 1,500) , Cyclohexyl, cyclopentyl, 2-heptylcyclohexyl, phenyl, na Phthyl, xenyl, p-heptylphenyl, 2,6-di-tert-butylphenyl, benzyl Phenylethyl, 3,5-dodecylphenyl, chlorophenyl, α-methoxy-β -Naphthyl, p-nitrophenyl, p-phenoxyphenyl, 2-bromomethyl, 3- Phenyl substituted with lorocyclohexyl and polypropylene (molecular weight of 300) Group.   The substantially hydrocarbon group substituted by hydroxy mainly has a hydroxy group. And the above hydrocarbon groups. Groups having less than about 8 carbon atoms are those whose hydro It is preferred because it is convenient for preparing xy-substituted triesters. Of such groups Examples are hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydro Xypropyl, 2-hydroxycyclohexyl, 2-hydroxycyclopentyl, 2- Hydroxy-1-octyl, 1-hydroxy-3-octyl, 1-hydroxy-2-octyl , 2-hydroxy-3-phenylcyclohexyl, 1-hydroxy-2-phenylethyl, 2-hydroxy-1-phenylethyl, 2-hydroxy-1-p-tolylethyl and 2-hydro It is a xy-3-butyl group. Other, substantially substituted, hydroxy-substituted hydrocarbon groups Examples are 2,5-dihydroxyphenyl, α-hydroxy-β-naphthyl, 3-hydroxy- 4-dodecyl, 3-hydroxy-6-octadecyl and p- (p-hydroxyphenyl) -phenyl Phenyl group.   A preferred class of hydroxy-substituted triesters has the structural formula Wherein R ″ is substantially the hydrocarbon group described above, and R ′ is a functional group as described above. Divalent substantial groups such as alkylene or arylene groups derived from hydrocarbon groups Is a hydrocarbon group) Is a triester having the formula: A convenient method for producing such esters is It relates to the reaction of sphorodithiophosphoric acid with epoxides or glycols. like that Reactions are well known in the art. The following equation illustrates the reaction. You. )   For reasons of economy, aliphatic epoxides and salts having less than about 8 carbon atoms Tylene oxide is preferred for use in the above method. Particularly useful epoki Sid is ethylene oxide, propylene oxide, styrene oxide, α-methyl Styrene oxide, p-methylstyrene oxide, cyclohexene oxide, Cyclopentene oxide, dodecene oxide, octadecene oxide, 2,3-butene Oxide, 1,2-butene oxide, 1,2-octene oxide, 3,4-penteneoxy And 4-phenyl-1,2-cyclohexene oxide. Glycol Include aliphatic and aromatic di-hydroxy compounds. The latter is hydroxy Exemplified by non, catechol, resorcinol and 1,2-dihydroxynaphthalene Is done. Ethylene glycol, trimethylene glycol, tetramethylene glyco , Decamethylene glycol, diethylene glycol, triethylene glycol And aliphatic glycols such as pentaethylene glycol are particularly useful. .   Other convenient methods for producing hydroxy-substituted triesters include phosphoro Dithioic acid, allyl alcohol, cinnamyl alcohol or oleyl alcohol And the method is described in U.S. Pat. No. 2,528,723. No. Another method involves replacing the metal salt of phosphorothioic acid with a halogen. The reaction with alcohols described is described in US Reissue Patent No. 20,411.   Phosphorodithioic acids from which hydroxy-substituted triesters can be derived are likewise well known. Have been. Phosphorodithioic acids react with phosphorus pentasulfide with alcohols or phenols. It is manufactured in response. The reaction is carried out with 4 moles of alcohol per mole of phosphorus pentasulfide or It requires phenol and is performed at temperatures ranging from about 50 ° C to about 200 ° C. Therefore, 0 , 0'-Di-n-hexyl phosphorodithioic acid is prepared by the reaction of phosphorus pentasulfide with 4 moles of n-hexyl About 2 hours at 100 ° C. in alcohol. Hydrogen sulfide is liberated, And the rest is the acid. The production of phosphoromonothioic acids is Achieved by treatment with thioic acid vapor. Phosphorotrithioic acid and phosphorotate Lathioic acids are mercaptans of phosphorus pentasulfide or mercaptans and alcohols. Obtained by reaction with a mixture of   Mixtures of phosphorus pentasulfide, phenols or alcohols (eg, 2: 1 weight ratio) Reaction between isobutanol and n-hexanol), two organic groups having different Sphorodithioic acid is produced. Such acids are also useful in the present invention .   Inorganic phosphorus useful in the reaction of phosphorothioic acids with hydroxy-substituted triesters The active substance is preferably phosphorus pentoxide. Other oxidations such as phosphorus trioxide and phosphorus tetroxide Phosphorus is useful as well. Phosphoric acid and phosphorus halides are also useful. They are phosphorus Acid, pyrophosphoric acid, metaphosphoric acid, hypophosphoric acid, phosphorous acid, pyrophosphorous acid, metaphosphorous acid, hypophosphorous acid , Phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, monobromophosphorus tetracloride), phosphorus oxychloride and phosphorus triiodide.   For the reaction of hydroxy-substituted triesters of phosphorothioic acids with inorganic phosphorous agents A more acidic product is produced. The chemical composition of the acidic product depends on the inorganic phosphorus used. Much depends on the nature of the active substance. In most cases, the product has a detailed composition Is an unknown complex mixture. But the reaction is Roxy groups are involved with inorganic phosphorus agents. At this point, the reaction is Similar to the reaction of alcohol or phenol with inorganic phosphorous agents. Therefore, The reaction of roxy-substituted triesters with phosphorus pentoxide is mainly due to the fact that the ester group is Acid, a residue obtained by removal of the hydroxy group of a thioic acid triester reactant To form a phosphoric acid ester, ie, a monoester or diester of phosphoric acid. The products can also include one or two phosphonic acids and carbon-phosphorus direct bonds present. And phosphinic acid.   Acidic production of the reaction of hydroxy-substituted tristres with phosphorus oxyhalides or phosphoric acids. The product is a similar mixture of acid phosphate, phosphonic acid and / or phosphinic acid Is considered to be generated. On the other hand, a hydroxy-substituted triester, phosphorus trichloride or It is believed that the reaction with phosphoric acid mainly produces acidic organic phosphites. Other Are obtained by the use of the other inorganic phosphorus acting substances indicated above. In any case Even so, the products are acidic and as such produce neutralized products useful in the present invention. Useful as an intermediate for construction.   Typically, from about 2 moles to about 5 moles of triester are used for each mole of inorganic phosphorous agent. Is used. The preferred proportion of triester is about It is 3 to 4 mol. Use of any reactant amounts outside the limits set forth herein Use results in excess amounts of unused reactants and is usually not preferred.   Inorganic phosphorus compounds of hydroxy-substituted triesters for producing acidic intermediates The reaction with the quality is carried out by heating the two reactants at a temperature approximately above room temperature, preferably at about 50 ° C. This is done by simply mixing at higher temperatures. More like 100 ℃ or 150 ℃ Higher temperatures can be used but are usually unnecessary.   Amines useful for neutralizing acidic intermediates include aliphatic amines, aromatic amines, It can be an alicyclic, heterocyclic or carbocyclic amine. About 4 Amines having up to about 30 aliphatic carbon atoms are preferred, with at least about 8 carbon atoms being preferred. Having the formula, R ″ -NH_TwoWherein R ″ is, for example, tert-octyl, tert-dodecyl , Tert-tetradecyl, tert-octadecyl, cetyl, behenyl, stearyl, d Icosyl, docosyl, tetracosyl, hexatriacontanil and pentahexa Aliphatic groups such as contanyl) are particularly useful. Examples of other aliphatic amines Include cyclohexylamine, n-hexylamine, dodecylamine, didodecyl A Min, tridodecylamine, N-methyl-octylamine, butylamine, beheni Ruamine, stearylamine, oleylamine, myristylamine and N-dodecy Rutrimethylenediamine, aniline, o-toluidine, benzidine, phenylene Amine, N, N'-di-sec-butylphenylenediamine, β-naphthylamine, α-naph Tylamine, morpholine, piperazine, menthanediamine, cyclopentylamine , Ethylenediamine, hexamethylenetetraamine, octamethylenediamine And N, N'-dibutylphenylenediamine. Also, ethanolamine, die Tanolamine, triethanolamine, isopropanolamine, p-aminophen Knol, 4-amino-naphthol-1, 8-amino-naphthol-1, β-aminoalizarari 2-amino-2-ethyl-1,3-propanediol, 4-amino-4'-hydroxydife Hydroxy-substituted amines such as nyl ether and 2-aminoresorcinol are also useful It is.   Of the various available hydroxy-substituted amines that can be used, hydroxy-substituted Aliphatic amines are preferred, in particular, most of the formulas Wherein R ″ is as defined above, and A is methylene, ethylene, 1,2-pro Pyrene, trimethylene, 1,2-butylene, tetramethylene, 1,3-amylene, penta X is 1 to 10, Q is hydrogen, (AQ)_xH or R " ) Is an amine having Often, such hydroxy-substituted aliphatic amines The use of the present invention imparts improved rust inhibiting properties to the phosphorus and nitrogen containing compositions of the present invention. . Examples of such preferred hydroxy-substituted aliphatic amines include N-4-hydroxybut Tildodecylamine, N-2-hydroxyethyl-n-octylamine, N-2-hydroxy Cypropyldinonylamine, N, N-di- (3-hydroxypropyl) -tert-dodecyl Amine, N-hydroxytriethoxyethyl-tert-tetradecylamine, N-2-hydrido Roxyethyl-tert-dodecylamine, N-hydroxyhexapropoxypropyl-t ert-octadecylamine, N-5-hydroxypentyl-di-n-decylamine, etc. I will. Convenient and for producing such hydroxy-substituted aliphatic amines Economical methods are preferably sodium methoxide, sodium amide, nato Aliphatic primary or secondary amines in the presence of a suitable catalyst such as , Known reactions with epoxides of at least approximately equal molecular weight.   In the above formula, R ″, x and A are as defined above. Particularly preferred The hydroxy-substituted aliphatic amine has the formula tert-R-NHAOH (where tert-R is A tert-alkyl group having about 11 to about 24 carbon atoms) It is an alkyl-substituted mono-tert-alkylamine. Formula, tert-R-NHAOH single Instead of the compound of, for example, ethylene oxide, propylene oxide or butyric Epoxides such as lenoxide, C₁₁-C₁₄Tert-alkyl primary amine Kind, C₁₃-C_{twenty two}Tert-alkyl primary amines such as tert-alkyl primary amines Mixtures of such compounds produced by reaction with commercially available mixtures of amines Is often convenient and desirable.   Neutralization of acidic intermediates with amines is mostly exothermic, Preferably by simply mixing the reactants at a temperature of about 0 ° C to about 200 ° C Can be. The chemical makeup of the neutralized product of the reaction is largely temperature dependent. about At relatively low temperatures, such as below 80 ° C, the product mainly forms salts with amine acids. Including. At temperatures above 100 ° C., the products are amides, amidines or their It may include a mixture. However, the reaction of the acidic intermediate with the tertiary amine only converts the salt Generate.   The relative proportions of the acidic intermediate and the amine used in the reaction are preferably Is such that a substantial proportion of the acidic intermediate is neutralized. Used for that reaction The minimum amount of amine to be produced depends mainly on the utility of many of the products produced . In most cases, enough acid to neutralize at least about 50% of the acidity of the intermediate Mi Required. For use as an additive in hydrocarbon oils, the acidity of the intermediate A substantially neutral product, such as that obtained by neutralization of at least about 90% of the No. Thus, the amount of amine used will depend on the desired acidity of the product and also For example, the acidity of the intermediate determined by ASTM operation display D-664 or D-974 Can vary more widely.   Particularly preferred amine phosphates are those in which the acidic intermediate is P_TwoO_FiveHydroxypropyl-0,0 When derived from reaction with -di (4-methyl-2-pentyl) phosphorodithioate It is. This acidic intermediate is then converted to C₁₂Or C₁₄Of tertiary aliphatic primary amines And can be neutralized or partially neutralized. An example of such an amine is Prim It is marketed under the trade name ene 81R.   An effective amount of the amine phosphate can be used in the compositions of the present invention, but typically The amine phosphate is present in the final MTF in an amount of 0.01 to 5% by weight, preferably 0.05 to 4% by weight. , Most preferably in an amount of 0.1 to 3% by weight.Neutral or acidic friction modifier   Friction modifiers useful in the present invention are those that are essentially neutral or acidic. . Friction modifiers that are substantially neutral, i.e., basic in relaxation, are also within the scope of the present invention. Think about it. However, friction modifiers that are essentially basic (eg, oleamide, Stearamide, etc.) do not form part of the present invention.   Examples of neutral friction modifiers include mono- and poly-carboxylic acids and their anhydrides, Includes alcohol esters and salts.   Acidic friction modifiers include mono- and poly-carboxylic acids and their anhydrides and moieties. Alcohol esters.   Examples of suitable monocarboxylic acids are fatty acids having 9 to 30 carbon atoms in the aliphatic chain. Is an acid. Examples of fatty acids include nonanoic acid (pelargonic acid), decanoic acid (capric acid) ), Undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (Myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), hepta Decanoic acid (margaric acid), octadecanoic acid (stearic acid or isostearin Acid), nonadecanoic acid, eicosanoic acid (arachinic acid), decenoic acid, undecenoic acid, Dodecenoic acid, tridecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid , Octadecenoic acid (oleic acid), eicosenoic acid or mixtures thereof are included.   Examples of suitable poly-carboxylic acids and their anhydrides are the dimers of the above-mentioned fatty acids. -Derivatives (eg, oleic acid dimer) and the hydrocarbyl substituent is C₁₂No To C₃₀It is a hydrocarbyl-substituted succinic anhydride which is an aliphatic hydrocarbyl group.   Particularly useful alcohols in the present invention have the structure, OH-R₁-OH (Where R₁Is C₁Or C₁₂An alkyl group of C₁Or C₁₂Alkylene group or C₆ Or C₂₀An aryl group of₁May be linear or branched, and a heteroatom (N , S or O) and may also include aromatic substituents) Is a diol represented by Preferred diols of the present invention are 1,4-butanediol , 1,5-hexanediol, thiodiglycol, dithiodiglycol, dietano And 1,2-propanediol.   Triol alcohols and their derivatives are also suitable for use in the present invention. Good A preferred triol is glycerol.   The friction modifier of the present invention is usually prepared by heating an acid or anhydride together with an alcohol, Produced by forming a stell or partial ester and removing the resulting water You. However, other manufacturing methods are known and can be used.   Examples of diol friction modifier esters are described in U.S. Pat.No. 4,702,850. C reacted with a diol₁₂Or C₃₀Of aliphatic hydrocarbyl substituted Succinic acid or anhydride, and metal salts thereof. The most preferred esters are It is a product of kutadecenyl succinic anhydride and thiodiglycol.   Examples of suitable friction modifiers formed from triols include the following structures, (I), ( II) and (III):   (Where R_TwoIs an aliphatic arsenic containing linear, saturated or unsaturated hydrocarbyl groups. Drocarbyl group, typically about 9 to about 29, preferably about 11 to about 23, Most preferred are aliphatic hydrocarbyl groups having about 15 to about 20 carbon atoms ) Is represented by As used herein, the term “hydrocarbyl” refers to pure Used to contain not only hydrocarbyl groups but also substantial hydrocarbyl groups. You. The description of those groups as being substantially hydrocarbyl groups refers to those groups Non-hydrocarbyl greatly affects hydrocarbyl properties with respect to description Means no substituents or non-carbon atoms.   Examples of triesters useful in the present invention include glycerol monooleate, Lycerol dioleate, glycerol monoisostearate, triglycerol Rudiisostearate, sorbitan monooleate, sorbitan sesquioleate Sorbitan trioleate, sorbitan stearate, sorbitan palmite It is. Preferred friction modifiers of this type used in the present invention are With lyserol monooleate and glycerol dioleate and their mixtures is there. Also suitable are their metal salts, especially copper salts.   The treatment ratio of the friction modifier of the present invention may be about 0.01 to about 5% by weight in the final MTF, preferably. Preferably it is in the range of 0.05 to 3% by weight, most preferably 0.05 to 1.5% by weight.   Other additives known in the art can be added to the lubricating oil. These additives include , Corrosion inhibitors, antioxidants, dispersants, antiwear agents, metal cleaners, extreme pressure additives, Le Swelling agents and the like are included. They are, for example, C.V. Smalheer and R. Kennedy Smith "Lubricant Additives" (1967), pp. 1-11 and U.S. Pat. No. 4,105,571. No. 1993.   Representative examples of those additives in fully formulated MTF are summarized below. You.   Suitable viscosity index improvers include C_TwoOr C₃₀Two or more monomers of the olefin And homopolymers and copolymers of Suitable olefins include α-olefin And straight-chain or branched, aliphatic or aromatic, alkyl Aromatic, alicyclic and the like. Often they are ethylene and C_ThreeOr C₃₀ Copolymers with olefins, particularly preferred are ethylene and propylene Is a copolymer of Polyisobutylene, C₆Α-olefins and higher α -Homopolymers and copolymers of olefins, atactic polypropylene, Hydrogenated polymers and copolymers of styrene with, for example, isoprene and / or butadiene Other polymers such as limers and terpolymers can also be used.   Other suitable viscosity index improvers include polyacrylates and polymethacrylates. And their derivatives. Particularly preferred is polymethacrylate .   Suitable corrosion inhibitors include 1,3,4-thiadiazole mercapto- and hydrocarbyl. Vilthio-disubstituted derivatives such as C_TwoOr C₃₀Of 1,3,4-thiadiazole , Aryl, cycloalkyl, aralkyl and alkaryl-mono- , Di-, tri- or tetra- or thio-disubstituted derivatives. Such a thing Examples of qualities include 2,5-bis (octylthio) -1,3,4-thiadiazole, 2,5-bis (octylthio) Octyldithio) -1,3,4-thiadiazole, 2,5-bis (octyltrithio) -1,3,4- Thiadiazole, 2,5-bis (octyltetrathio) -1,3,4-thiadiazole, 2,5 -Bis (nonylthio) -1,3,4-thiadiazole, 2,5-bis (dodecyldithio) -1,3 1,4-thiadiazole, 2-dodecyldithio-5-phenyldithio-1,3,4-thiadiazole , 2,5-bis (cyclohexyldithio) -1,3,4-thiadiazole and mixtures thereof Compounds are included.   Preferred corrosion inhibitors are U.S. Patent Nos. 2,719,125, 2,719,126 and 3,087,932. 1,3,4-thiadiazole derivatives such as the compounds described in No. Especially preferred What's new is the 2,5-bis (t-octyldithio) -1,3, 4-thiadiazole, 2,5-bis (t-nonyldithio), commercially available as Amoco 158 ) -1,3,4-thiadiazole, 2-nonyldisulfide-5-mercapto-1,3,4-thiashi Azoles and mixtures thereof.   Suitable seal swell agents include 8-13 carbon atoms, such as tridecyl alcohol. Mineral oils of the type that cause swelling, including aliphatic alcohols having a child, are included. Good Preferred seal swelling agents are disclosed in US Pat. No. 3,974,081. Oil-soluble, saturated, aliphatic or aliphatic having up to 60 carbon atoms and 2 to 4 bonds Are aromatic and hydrocarbon esters such as dihexyl phthalate.   Useful antioxidants are ashless antioxidants such as arylamines and phenols And metal-containing antioxidants such as dialkyldithiophosphates.   Ashless antioxidants useful in the present invention are arylamines or phenols. Amine-type antioxidants include phenyl-α-naphthylamine and diphenylamine , Phenothiazine, p-phenylenediamine, alkylated diphenylamine [eg For example, the alkyl groups each have from 8 to 12 carbon atoms of p, p'-bis (alkylphenyl Nil) Noll-based antioxidants include sterically hindered phenols (eg, 2,6-di-t-butyl). Butylphenol, 4-methyl-2,6-di-t-butylphenol) and bisphenols [4,4'-methylenebis (2,6-di-t-butylphenol), such a substance is , 2,6-di-t-butylphenols, which include 3,5-di-t-butyl-4-hydrido. B).   Metal-containing zinc dithiophosphate antioxidants include alcohols, P_TwoO_FiveReaction with Produced by producing alkyldithiophosphoric acid and then neutralizing with zinc oxide. The production of zinc dithiophosphate is well known and has been discussed in many published literature. Have been. For example, Lezius-Hiles Co. (Cleveland, Ohio) Issued by C.V. Smalheer and R.K. “Lubricant Additives” by Smith ( 1967) and Noyes Data Corp. (Park Ridge, New Jersey) See "Lubricant Additives" (1973) by M.W. Examples of such materials are zinc (diisooctyldithiophosphate) and (di-2-ethyl). Hexyldithiophosphate).   Other suitable antioxidants include P_TwoO_FiveIncludes treated terpenes and their derivatives You. Examples of suitable terpenes include turpentine, pine oil and dipentenes Containing, the formula, C_TenH₆Terpene hydrocarbons having the formula Includes various, synthetic and naturally occurring oxygen-containing derivatives. Especially preferred The lupen compound is α-pinene. Therefore, a preferred antioxidant is polyisobuteni P reacted with succinimide dispersant_TwoO_FiveTreated α-pinene.   Foam control is achieved by using polysiloxane compounds such as silicone oil and polydimethylsiloxane. Provided by roxane.   Suitable dispersants include hydrocarbyl succinimide, hydrocarbyl succinic acid Amides, mixed esters / amides of hydrocarbyl-substituted succinic acids, Hydroxy esters of ruville-substituted succinic acids and hydrocarbyl-substituted phenols , Formaldehyde and Mannich condensation products of polyamines. Hinoyo Mixtures of such dispersants are also used.   A preferred dispersant is alkenyl succinimide. They include patent literature Formed using various amines or amine derivatives as widely disclosed in Acyclic hydrocarbyl-substituted succinimides. The inorganic acid of phosphorus (or its Use of alkenyl succinimides treated with anhydrides) and with a borating agent Elasts made from materials such as oroloelastomers and silicon-containing elastomers Very compatible with tomeric seals, suitable for use in compositions of the present invention ing. Polyisobutenyl succinic anhydride and triethylene tetraamine or Poly (ethylene) produced from an alkylene polyamine such as triethylenepentamine A number average molecule having an isobutenyl substituent of 500 to 5,000 (preferably 800 to 2.500) Polyisobutenyl succinimides derived from polyisobutene having an amount of Particularly suitable. Dispersants can be post-treated with many agents known to those skilled in the art. . (See, for example, U.S. Patent Nos. 3,254,025, 3,502,677, and 4,857,214.)   Suitable metal-containing detergents include one or more of the following acidic substances (or mixtures thereof): : (1) sulfonic acid, (2) carboxylic acid, (3) salicylic acid, (4) alkylphenol (5) sulfurized alkylphenol, (6) at least one direct carbon-phosphorus bond. Oil solubility of alkali metal or alkaline earth metal with organic phosphoric acid characterized Are exemplified by neutral or overbased salts of Such organic phosphoric acids include Phosphorus trichloride of a polymer (eg, polyisobutylene having a molecular weight of 1,000) , Phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, yellow phosphorus and sulfur halide, or phosphorous chloride Includes compounds produced by treatment with a phosphating agent such as holothioic acid. That's it The preferred salts of oxalic acid from a cost-effective, toxic and environmental standpoint are sodium and potassium. And salts of lithium, calcium, and magnesium. Useful in the present invention Preferred salts are neutral or overbased salts of calcium or magnesium.   Oil-soluble, neutral metal-containing detergents are formulated based on the amount of acid present in the detergent. A cleaning agent that contains a stoichiometric amount of metal. Therefore, in general, a neutral wash The agents have a low basicity when compared to their overbased counterparts. Like that Acidic substances used to produce various cleaning agents include carboxylic acids and salicylic acids. , Alkylphenols, sulfonic acids, sulfurized alkylphenols, etc. You.   The term "overbased" in relation to metallic detergents is more stoichiometric than organic groups It is used to represent a metal salt in which a large amount of metal is present. Produce overbased salts A commonly used method is to prepare a mineral oil solution of the acid in stoichiometric excess, Metal neutralizers such as metal oxides, hydroxides, carbonates, and bicarbonates Heating at a temperature of 50 ° C. and filtering the resulting product.   Examples of suitable metal-containing detergents include each aromatic group to impart hydrocarbon solubility. Having one or more aliphatic groups, lithium phenates, sodium phenate , Potassium phenate, calcium phenate, magnesium phenate , Lithium sulfide phenates, sodium sulfide phenates, potassium sulfide Phenates, calcium sulfide phenates and magnesium sulfide phenates; Each sulfonic acid moiety is attached to an aromatic nucleus, which also confers hydrocarbon solubility. Lithium sulfonates having one or more aliphatic substituents, Thorium, potassium sulfonate, calcium sulfonate and sulfonate Gnesiums; fats having usually one or more aromatic moieties for imparting hydrocarbon solubility Lithium salicylates and sodium salicylate substituted by an aliphatic substituent , Potassium salicylate, calcium salicylate and magnesium salicylate And hydrolyzed phosphorous sulfides having 10 to 2,000 carbon atoms (phosp hosulfurized) olefins or hydrolysed phosphorosulfurized alcohols and / or Lithium and sodium salts of aliphatic substituted phenolic compounds having up to 2,000 carbon atoms , Potassium, calcium and magnesium salts; aliphatic carboxylic acids and aliphatics Lithium, sodium, potassium, calcium and mug of substituted alicyclic carboxylic acids Nesium salts; and many other similar alkali metal salts and alkaloids of oil-soluble organic acids. These include neutral and overbased salts such as potassium earth metal salts. Not limited. Two or more different alkali metal salts and / or alkaline earth metal salts Mixtures of neutral or overbased salts of can also be used. Similarly, two or more different Neutral and / or overbased salts of the mixture of acids (eg, one or more overbased calcium salts). Mufenate and one or more overbased calcium sulfonates) are also used.   As is well known, overbased metal detergents are probably microdispersions or It is generally considered to contain an overbased amount of inorganic base in the form of a colloidal suspension I have. Therefore, the term “oil-soluble” used in metal-based detergents is a term used for inorganic salts. The exact meaning of the term is intended to include metal detergents in which the group is present It need not be completely or truly oil-soluble in the Cleaning agent such as is completely and completely dissolved in the base oil. It is intended to include metal detergents, which are mobile detergents.   In summary, the various metal-based detergents described above are sometimes simply neutral, basic, Or overbased alkali metal- or alkaline earth metal-containing organic acid salts. You.   Oil-soluble neutral and overbased metal detergents and alkaline earth metal-containing detergents Methods for producing are well known to those skilled in the art and have been extensively reported in the patent literature. You. For example, U.S. Pat.Nos. 2,001,108, 2,081,075, 2,095,538, 2,144 No. 2,078, No. 2,163,622, No. 2,270,183, No. 2,292,205, No. 2,335,017, No. 2, No. 399,877, No. 2,416,281, No. 2,451,345, No. 2,451,346, No. 2,485,861, No. 2,501,731, No. 2,501,732, No. 2,585,520, No. 2,671,758, No. 2,616,904 No. 2,616,905, 2,616,906, 2,616,911, 2,616,924, 2,616, No. 925, No. 2,617,049, No. 2,695,910, No. 3,178,368, No. 3,367,867, No. 3,4 No. 96,105, No. 3,629,109, No. 3,865,737, No. 3,907,691, No. 4,100,085, No. No. 4,129,589, No. 4,137,184, No. 4,184,740, No. 4,212,752, No. 4,617,135 Nos. 4,647,387 and 4,880,550.   The metal-based detergent used in the present invention may be, if desired, an oil-soluble borated neutral. And / or overbased alkali metal- or alkaline earth metal-containing detergents . A method for producing a boronated metal-based detergent is described, for example, in US Pat. No. 80,548, No. 3,679,584, No. 3,829,381, No. 3,909,691, No. 4,965,003, No. No. 4,965,004.   The preferred metal-based detergent used in the present invention is an overbased calcium sulfide sulfide. Nart, overbased magnesium sulfide phenate, overbased sulfonic acid calcium And overbased magnesium sulfonate.   The additive formulations of the present invention can be combined with other desirable lubricating oil additives to form concentrated Generate a contraction. Typically, the active ingredient (ai) content of the concentrate is 30% of the concentrate. To 100% by weight, preferably 40 to 95% by weight, most preferably 50 to 90% by weight. Range. The balance of the concentrate is typically a diluent consisting of lubricating oil or solvent. It is.   The shift durability properties of the present invention are tested on a Hurth synchromesh rig Is done. Briefly, the Haas test rig consists of two speed changing gears and two Consists of a shring. The ring achieves interlocking (ie, gear shifting Before it works to equalize the speed of the input and output gears, Bronze (less durable) or chemically treated sintered material (more durable) ). Motor gives drive, two flywheels add inertia Used to do. During the test cycle, one of the synchromesh rings Slow down one of the flywheels, stop it before engaging the gears, and then A ring mesh ring increases the speed of the same flywheel and engages other gears. Sinking enough to prevent smooth and fast shifting at the end of the test This test cycle is repeated until the romesh ring wears.   The additive formulation of the present invention, with a hearth rig having a brass synchromesh ring Tested and reported up to 100,000 cycles. Currently commercially available fluids are 2,000 to 15,000 units using a brass or bronze synchromesh ring Fluids that have failed the Haurs test for the cycle and will perform up to 100,000 Haas cycles Means a very shift-resistant fluid. Sintered which is more durable Even when using a synchromesh ring, commercially available products range from 40,000 to 70,0 Hearth loss in the range of 00 cycles could only be performed. Therefore, the book Excellent shifting properties of the transmission fluid of the invention were demonstrated.   The principles, preferred embodiments and modes of operation of the present invention have been described herein. I However, the particular forms disclosed should be considered as illustrative, not limiting. As such, the invention to be protected herein is limited to the particular forms disclosed. Should not be interpreted as being. Modifications and changes without departing from the spirit of the invention Can be made by those skilled in the art.

[Procedure of Amendment] Article 184-8, Paragraph 1 of the Patent Act [Date of Submission] October 9, 1997 [Content of Amendment] Claims (1) neutralization of (a) an aliphatic primary amine and a hydroxy-substituted triester of a phosphorothioic acid treated with an inorganic phosphorous agent in an effective amount to improve shift durability; Or (b) (i) alcohol esters and salts of mono- and poly-carboxylic acids and their anhydrides, (ii) mono- and poly-carboxylic acids and their Anhydrides and their partial alcohol esters, the composition of which comprises a neutral or acidic friction modifier which does not contain a Group I or II metal salt of a borated overbased organic acid. A fluid composition for a power transmission, comprising an agent composition. 2. The composition according to claim 1, wherein the lubricating oil is a mineral oil, a poly-α-olefin or a mixture thereof. 3. 3. The composition according to claim 1 or claim 2, wherein the additive formulation further comprises mercapto- and hydrocarbylthio-disubstituted derivatives of 1,3,4-thiadiazole and mixtures thereof. 4. Additive formulation, the ashless, metal-containing, P further includes a ₂ O ₅ treated terpene derivative or an antioxidant mixtures thereof, according to any one claims of claims 1 to 3 Composition. 5. The composition according to any one of claims 1 to 4, wherein the composition is a fluid for a manual transmission. 6. An additive concentrate comprising a major amount of the additive formulation of claim 1 and other desirable lubricating oil additives, as well as a minor amount of lubricating oil. 7. A method for improving the shift durability of a transmission fluid by incorporating an effective amount of the additive concentrate according to claim 6 into the transmission fluid.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 163/00 C10M 163/00 169/04 169/04 // C10N 30:06 40:00 40:04 40:08 (72) Inventor Humphrey, Robert Walter United Kingdom, Berkshire ARG 15.0 Quex, Newbury, Ink Penn, Upper Green, Benetict House (no address) (72) Inventor Dowling, Michael United Kingdom, Berkshire ARG 8. 9 El H, Street Ray, Townsend Road, “Shevioc” (No Street)

Claims (1)

[Claims] 1. For transmissions comprising (1) a large amount of lubricating oil and (2) an effective amount of an additive compound comprising (a) amine phosphate and (b) a neutral or acidic friction modifier to improve shift durability. Fluid composition. 2. The composition according to claim 1, wherein the lubricating oil is a mineral oil, a poly-α-olefin or a mixture thereof. 3. 3. The composition of claim 2, wherein the amine phosphate is a neutralized or partially neutralized product of an aliphatic primary amine and a hydroxy-substituted triester of a phosphorothioic acid treated with an inorganic phosphorous agent. 4. The composition according to claim 3, wherein the friction modifier is a complete or partial alcoholic ester of a mono- or poly-carboxylic acid. 5. The composition of claim 4, wherein the additive formulation further comprises a mercapto- and hydrocarbylthio-disubstituted derivative of 1,3,4-thiadiazole and mixtures thereof. 6. Additive formulation, the ashless, metal-containing, further comprising an antioxidant which is the P ₂ O ₅ treated terpene derivative, or mixtures thereof The composition of claim 5. 7. 7. The composition of claim 6, wherein the composition is a manual transmission fluid. 8. An additive concentrate comprising a major amount of the additive of claim 1 and other desirable lubricating oil additives and a minor amount of lubricating oil. 9. A method for improving the shift durability of a transmission fluid by incorporating an effective amount of the additive concentrate according to claim 8 into the transmission fluid.