JP2753585B2 - Friction-modifying oily concentrates with improved stability - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to oil-soluble additive mixtures useful in fuel oil and lubricating oil compositions, concentrates containing the additives, and methods of making and using them. This additive mixture
Includes a boron-free ashless dispersant, a copper antioxidant and a friction modifier with improved storage stability.

BACKGROUND OF THE INVENTION Hitherto, many lubricating oils and fuels contain compounds known as friction modifiers (also called "lubricants"). These compounds serve to reduce the friction of internal combustion engine components and thereby improve fuel economy. U.S. Patent No. 3,429,817, about 2 moles of C ₂ -C ₅ glycols about 1 mole of C ₁₈ unsaturated fatty acid (e.g., linoleic acid or oleic acid) is formed by reacting a C ₃₆ dicarboxylic acid dimer The present invention relates to improving the lubricity and load bearing capacity of a synthetic ester lubricating oil by adding an ester. U.S. Pat. No. 3,273,981 is directed to fuel oils and lubricating oils containing a mixture of dimer acid and a polyhydric alcohol partial ester as a lubricating additive.
U.S. Pat. No. 4,459,223 relates to lubricating oil friction reducing additives that are the reaction products of dimer carboxylic acids (eg, linoleic acid dimers) with polyhydric alcohols having at least three hydroxyl groups. US Patent 4,479,883
No. is a polycarboxylic acid (eg, linoleic acid dimer)
Glycol or glycerol ester of Mo, Zn or Sb
The present invention relates to lubricating oil compositions having relatively low phosphorus rail and improved friction reducing properties by use of a mixture with dithiocarbamates. U.S. Pat. No. 4,557,846 relates to a lubricating oil friction reducer consisting of an oil-soluble hydroxyamide compound prepared by condensing a dimer carboxylic acid (eg, linoleic acid dimer) with a hydroxyamine. U.S. Patent No. 4,617,026, the hydroxyl of the C ₁₂ -C ₃₀ monocarboxylic acid and a glycol or trihydric alcohols (Thisゝa glycol may consist polyalkylene glycols having 2 to 100 oxyalkylene repeat units) The present invention relates to a fuel friction modifier comprising a contained ester. U.S. Patent No. 4,683,069 relates to lubricating oil fuel economy improving agent consisting of glycerol partial ester of C ₁₆ -C ₁₈ fatty acids.

The instability of compositions containing polycarboxylic acid-glycol esters, ashless dispersants and certain metal lubricating oil additives, and therefore the need for stabilization, is of interest in the art. U.S. Pat. No. 4,105,571 discloses a storage-stable lubricating oil composition comprising zinc dihydrocarbyl dithiophosphate, an ester of a polycarboxylic acid and a glycol and an ashless high molecular weight dispersant having improved abrasion and abrasion resistance. In ゝ, either the zinc component or the ester component or both are predispersed with the ashless dispersant prior to addition to the lubricating oil composition). These friction reducing esters are disclosed to include linoleic acid dimers that are esterified with a glycol such as diethylene glycol.

U.S. Pat.No. 4,388,201 discloses that a polycarboxylic acid-glycol friction modifier ester can be boronated or boron-free by adding a small proportion of an auxiliary dispersant consisting of an oil-soluble hydrocarbyl-substituted mono- or bisoxazoline or lactone oxazoline. Disclosed are lubricating oil compositions containing in combination with the treated alkenyl succinimide.

U.S. Patent No. About. Storage stability has been improved by the addition of small proportions of polyols or anhydride partial esters, amines or amides of fatty acids or ethoxylated fatty acids.

U.S. Patent No. It relates to a lubricating oil composition.

U.S. Patent No. 4,684,473, C ₄ ~C ₂₃ in the lubricating oil composition
It relates to solubilizing oxygenated (hydroxyl) esters of dimer acids (including linoleic acid dimer esters of polyhydric alcohols) by incorporating oil-soluble alkanols or oil-soluble alkyl phosphates. It is disclosed that the choice of alcohol chain length is critical.

EP 24,146 relates to lubricating oil compositions containing an oil-soluble copper compound in an amount sufficient to retard or inhibit oxidation of the lubricating oil in use, and wherein such lubricating oil compositions comprise from 1 to 10 It discloses that the composition may further comprise a weight percent of an ashless dispersant compound. Dispersants derived from polyisobutenyl succinic anhydride and polyethyleneamine are preferred. This dispersant is used in an amount of about 0.1 per mole of the acylated nitrogen compound.
It can be further modified with a boron compound to provide a 1 to 10 atomic ratio of boron. In addition, the patent discloses that the lubricating oil composition comprises a rust inhibitor such as lecithin, sorbitan monooleate, dodecyl succinic anhydride or an ethoxylated alkylphenol and other additives such as pour point depressants, viscosity index improvers, and the like. (For example, zinc dialkyldithiophosphate), a basic alkaline earth metal detergent, and the like. Examples of oil-soluble copper compounds include copper dihydrocarbyl thio - or dithiophosphate, synthetic or natural carboxylic acids (e.g., C ₁₀ -C ₁₈ fatty acids, oleic acid, naphthenic acid)
And the like.

U.S. Pat. No. 4,552,677 discloses copper salts of substituted succinic anhydride derivatives having a hydrocarbon substituent containing from about 8 to about 35 carbon atoms (the patentees acknowledge that these compounds are useful for crankcase lubricants). (Which has been shown to be an effective antioxidant).

U.S. Pat. No. 3,509,052 discloses lubricating oils, dispersants (which are derivatives of substituted succinic acids whose substituents contain at least 50 aliphatic carbon atoms) and demulsifiers such as polyoxyalkylene polyols. , Such as rust inhibitors, antioxidants and corrosion inhibitors. The dispersant may be a metal salt of an alkyl-substituted succinimide or substituted succinic acid post-treated with boron, wherein the metal is preferably
Group II metals, which are Al, Pb, Sn, Co, Ni or Zn).

EP 92,946 relates to a combination of an oil-soluble copper compound and a glycerol fatty acid ester as a fuel economy improver.

U.S. Pat. We handle lubricating oils containing 50-100 ppm copper together with oil-soluble organic sulfur compounds to provide a safe lubricating oil. U.S. Pat.Nos. 2,343,756 and 2,356,662,
It discloses that a copper compound is added to a lubricating oil in combination with a sulfur compound. In U.S. Pat. No. 2,552,580, cuprous thiosulfate is included in lubricating oil compositions at relatively high levels resulting in undesirably high sulfated ash content. U.S. Pat. No. 3,346,493 uses various polymeric amine-metal reactants in lubricating oil compositions. In two separate cases, where the metal is copper and the composition contains zinc dihydrocarbyl dithiophosphate, the amount of copper used is outside the scope of the invention, or the oil-insoluble copper compound is complexed with a dispersant. It is necessary to let
U.S. Pat. No. 3,652,616 discloses various polymeric amine-metal reactants for addition to lubricating oil compositions.
U.S. Pat. No. 4,122,033 discloses a whole group of transition metal compounds as additives for lubricating oils.

U.S. Pat.No. 3,271,310 relates to metal salts of alkenyl succinic acids, but these compounds are disclosed as being useful as detergents and rust inhibitors in hydrocarbon oils and in hydrocarbon substituents. At least about
It consists of a metal salt of a hydrocarbon-substituted succinic acid containing 50 aliphatic carbon atoms, wherein the metal consists of Group I, Group II, aluminum, lead, tin, cobalt or nickel. These salts are disclosed to be useful in amounts from 0.1 to about 20% by weight in lubricating oils and in amounts from 0.5 to about 5% by weight in lubricating oil compositions for use in gasoline internal combustion engines. ing. It is also disclosed that this salt is useful in combination with ashless dispersants, including those that have been boronated by reaction with boric acid.
It is further stated that the salts are useful as emulsifiers in water / oil emulsions and that when used as such, other emulsion additives such as rust inhibitors can be used. I have.

U.S. Pat. No. 3,351,647 relates to phosphorus and nitrogen containing reaction products formed by reacting a metal salt of phosphinodithioic acid with an amine such as an aliphatic amine having 1 to about 40 carbon atoms. Among the group of metals disclosed as useful is copper. These compounds are disclosed as additives for lubricating oils and automatic transmission fluids, which act as antioxidants and antiwear additives. These compounds are also stated to be useful in combination with ashless dispersants, such as the reaction product of triethylenetetramine with an alkenyl-substituted succinic anhydride having at least 50 carbon atoms in the alkenyl substituent. I have.

U.S. Pat. No. 3,401,185 relates to metal salts of phosphoric acids (including copper salts of such acids) useful in lubricating oils in combination with ashless dispersants, which may be boronized.

U.S. Pat. No. 3,328,298 relates to metal (eg, copper) containing compounds formed by reacting a basic inorganic metal compound with an intermediate obtained by reacting a phosphorothioic acid diester with an equimolar amount of an epoxide. The resulting metal-containing compounds are disclosed to be useful in combination with ashless dispersants.

U.S. Pat. No. 4,417,990 relates to a mixed metal salt / sulfide phenate composition.

U.S. Pat. No. 4,664,822 relates to certain copper metal-containing compounds, which disclose that these compounds are useful in combination with other additives, and that the additives include ashless dispersants (such as Can be boronized), zinc dialkyldithiophosphates, ash containing detergents and ashless rust inhibitor additives.

Canadian Patent No. 1,189,367 describes transition metal salts of organic acids,
The present invention relates to a hydrocarbon-soluble composition containing a hydrocarbon-soluble ashless dispersant and a phenolic antioxidant.
The composition may further comprise a dye, a metal deactivator and especially a demulsifier. Among the listed transition metal salts are copper organic acids, which include carboxylic, sulfonic and phosphorus acids. The transition metal salts used in this invention are described as being optionally overbased and containing one equivalent excess of metal per equivalent of acid-derived moiety.

U.S. Pat. No. 4,552,677 relates to copper salts of hydrocarbyl-substituted succinic acids wherein the hydrocarbon group contains from about 8 to about 35 carbon atoms. Such copper salts are said to be effective antioxidants for crankcase lubricants without detrimentally affecting the copper / lead corrosion behavior associated with rust and copper oleate. This is explained in the previously mentioned European Patent No. 24,146. Also, U.S. Pat.
The copper salt of 552,677 is said to be useful in combination with other additives, including ashless dispersants, which can be boronized.

U.S. Pat. No. 4,664,822 relates to a lubricating oil composition comprising an ashless dispersant, a composition containing 0.1 to 1.5% by weight of a copper overbased metal as a dispersant / cleaner, an antioxidant and a rust inhibitor. It is disclosed that the ashless dispersant can be boronated and that the lubricating oil composition can contain additional conventional additives (for example, friction modifiers are mentioned). Disclosed as suitable friction modifiers are esters such as monoesters from triglycerides or periols, esters such as glycol monooleate and pentaerythritol monooleate, and amides such as oleamide or amides made from polyamines or alkanolamines. Fatty acid derivatives consisting of amides, and heterocyclic compounds made by condensing compounds such as aminoquanidine with carboxylic acids to form triazoles. Further disclosed as suitable friction modifiers are Mo compounds and combinations of Na sulfonates (or Mo compounds) with glycerol monooleate and other fatty acid derivatives.

SUMMARY OF THE INVENTION According to the present invention, there is provided an improvement comprising a combination of (A) an ashless dispersant, (B) a friction modifier comprising a glycol ester or a hydroxyamine derivative of a polycarboxylic acid, and (C) an oil-soluble copper antioxidant. A friction adjusted oily composition having improved storage stability, wherein the oily composition is substantially free of boron and has a B: Cu weight ratio of less than about 0.6: 1. .

Surprisingly, the use of oil-soluble copper carboxylate antioxidants, such as copper oleate and copper salts of polyalkylene-substituted succinic anhydrides, such that the composition is substantially free of boron. The storage stability (i.e. the tendency for the formation of sediments and haze) in such compositions, especially in the concentrates to be used for the preparation of such compositions. Was found to be reduced.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oil composition comprising (A) an ashless dispersant, (B) a glycol ester and / or a hydroxyamide derivative of certain polycarboxylic acids and (C) an oil-soluble copper antioxidant compound. A composition, which is substantially free of boron.

As used herein, the expression "substantially free of boron" means a boron concentration of less than 30 ppm (by weight). Preferably, the boron concentration in the composition of the present invention is 20
It is less than ppm (weight ratio), more preferably less than 10 ppm (weight ratio).

Component A-Ashless Dispersants Ashless nitrogen or ester containing dispersants useful in the present invention include (i) oil soluble salts of long chain hydrocarbon substituted mono- and dicarboxylic acids or their anhydrides, amides, imides, oxazolines and An ester or a mixture thereof, (ii) a long-chain aliphatic hydrocarbon directly bonded to a polyamine, and (ii)
i) about 1 mole ratio of long chain hydrocarbon-substituted phenol to about 1
~ 2.5 moles of formaldehyde and about 0.5-2 moles of a polyalkylene polyamine formed by condensation with a Mannich condensation product wherein the long chain hydrocarbon groups in (i), (ii) and (iii) are _{2 to} C ₁₀ e.g. C ₂ to
A polymer of C ₅ monoolefin, consisting of boron non含物quality selected from the group consisting of those having a number average molecular weight of from about 300 to about 5,000).

A (i) As long-chain hydrocarbyl-substituted dicarboxylic acid-forming substances or acids, anhydrides or esters used in the present invention, long-chain hydrocarbons, generally polyolefins, are typically on average about 0.8 useful per mole of polyolefin. 1.0 to 2.0 (e.g. 1.0 to 1.6), preferably about 1.1 to
1.4 (e.g. 1.1-1.3) moles of α- or β-unsaturated C
₄ -C ₁₀ dicarboxylic acids, their anhydrides or esters such as fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloro maleic acid, fumaric acid dimethyl, chloro maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, And those substituted with cinnamic acid and mixtures thereof.

Unsaturated dicarboxylic acids, preferred olefin polymers for reaction with the anhydride or ester is a C ₂ -C ₁₀ for example polymers containing C ₂ -C ₅ monoolefin majority molar amount. Examples of such an olefin include nylene, propylene, butylene, isobutylene, pentene, octene-1, and styrene. The polymer may be a homopolymer such as polyisobutylene, or a copolymer of ethylene and propylene, a copolymer of butylene and isobutylene, or a copolymer of two or more such olefins such as a copolymer of propylene and isobutylene. It may be united. As other copolymers,
Minor molar amount eg from 1 to 10 mol% of the monomers of the copolymer C ₄ ~
Examples thereof include _C18 non-conjugated diolefins, such as a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene, and 1,4-hexadiene.

In some cases, the olefin polymer may be fully saturated, for example, an ethylene-propylene copolymer made by Ziegler-Natta synthesis using hydrogen as the molecular weight regulator.

Olefin polymers are usually from about 700 to about 5,000, for example 700
It has a number average molecular weight in the range of about 3,000, preferably about 800 to about 2,500, and therefore usually has an average of about 50 to 400 carbon atoms. A particularly useful olefin polymer is about 900
Number average molecular weight in the range of ~ 2,500 and about 1 per polymer chain.
Has two terminal double bonds. A particularly useful starting material for the high latency dispersants prepared according to the present invention is polyisobutylene.

Methods for reacting olefin polymers with _C4-10 unsaturated dicarboxylic acids, anhydrides or esters are known in the art. For example, an olefin polymer and a dicarboxylic acid material can simply be heated together to cause a thermal "ene" reaction, as disclosed in U.S. Patent Nos. 3,361,673 and 3,401,118. Alternatively, the olefin polymer can be first halogenated, e.g., chlorine or bromine in the polyolefin at a temperature of 60-250C, e.g.
By passing through for 7 hours, about 1 to about 1% based on the weight of the polymer is obtained.
It can be chlorinated or brominated to 8 preferably 3 to 7% by weight of chlorine or bromine. The halogenated polymer is then reacted with enough unsaturated acid or anhydride so that the resulting product contains about 1.0-2.0, preferably 1.1-1.4, e.g., 1.2 moles of unsaturated acid per mole of halogenated polymer. Thing and 100
The reaction can be carried out at a temperature of about 180 to 220 ° C for about 0.5 to 10 hours, for example, 3 to 8 hours. Methods of this general type are described in U.S. Pat. Nos. 3,087,436 and 3,172,892.
No. 3,272,746 and the like.

Alternatively, the olefin polymer and unsaturated acid material are mixed and heated while adding chlorine to the hot material.
This type of method is disclosed in U.S. Pat.Nos. 3,215,707 and 3,23.
No. 1,587, No. 3,912,764, No. 4,110,349, No. 4,2
No. 34,435 and British Patent 1,440,219.

Through the use of halogens, typically about 65-95% by weight of the polyolefin, for example polyisobutyle, reacts with the dicarboxylic acid material. If the thermal reaction is carried out without the use of halogens or catalysts, usually only about 50-75% by weight of the polyisobutylene will react. Chlorination helps to increase reactivity. For convenience, the functionality ratio of the dicarboxylic acid-forming units to the polyolefin (e.g., 1.0 to 2.0, etc.) is based on the total amount of polyolefin, i.e., the total amount of reacted and unreacted polyolefins present in the product formed by the reaction. Based.

Amine compounds useful for neutralizing hydrocarbyl-substituted dicarboxylic acid materials have about 2 to 60 (eg, 2 to 6)
) Preferably 2 to 40 (eg 3 to 20) total carbon atoms and about 1 to 12 (eg 2 to 9) preferably 3 to
Includes twelve most preferably mono- and polyamines having 3 to 9 nitrogen atoms. These amines may be hydrocarbylamines or may be hydrocarbylamines containing other groups such as hydroxyl, alkoxy, amide, nitrile, imidazoline and the like. Particularly useful are hydroxyamines having 1 to 6 hydroxyl groups, preferably 1 to 3 hydroxyl groups. Preferred amines have the general formula Wherein R, R ′, R ″ and R are each hydrogen, C _1-
C ₂₅ linear or branched alkyl group, C ₁ -C ₁₂ alkoxy C ₂ ~
C ₆ alkylene group, are each chosen from C ₂ -C ₁₂ hydroxy amino alkylene radicals, and C ₁ -C ₁₂ alkylamino C ₂ -C ₆ group consisting of alkylene group, R represents further wherein Wherein R 'is as defined above, and s and s' are 2-6, preferably 2
May be the same or different numbers, and t and t 'may be the same or different numbers, and are numbers from 0 to 10, preferably 2 to 7, and most preferably about 3 to 7, provided that t and t The sum of t 'shall not be greater than 10.]. To ensure an easy reaction, R, R ', R ", R, s, s', t and t'
Is selected in a manner sufficient to provide the compounds of formulas Ia and Ib typically with at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. Is preferred. This can be accomplished by selecting at least one of the R, R ', R "or R groups to be hydrogen, or when R becomes H or the Ic moiety has a secondary amino group. The most preferred amine of the above formula is represented by the formula Ib and has at least two primary amino groups and at least one, preferably at least three, t. Contains two secondary amine groups.

Examples of suitable amine compounds include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, polyethylene amines such as diethylene triamine, triethylene Ethylenetetramine, tetraethylenepentamine, polypropyleneamine such as 1,2-propylenediamine, di (1,2-propylene) triamine, di (1,3-propylene) triamine, N, N-dimethyl-1,3-diaminopropane , N, N-di (2-amineethyl) ethylenediamine,
N, N-di (2-hydroxyethyl) -1,3-propylenediamine, 3-dodecyloxypropylamine, N-dodecyl-1,3-propanediamine, trishydroxymethylaminomethane (THAM), diisopropanolamine,
Diethanolamine, triethanolamine, mono-,
Di- and tritallowamines, aminomorpholines such as N
-(3-aminopropyl) morpholine and the like.

Other useful amine compounds are alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane, heterocyclic nitrogen compounds such as imidazoline, and the general formulas Wherein p ₁ and p ₂ are the same or different and are each an integer of 1 to 4, and n ₁ , n ₂ and n ₃ are the same or different and are each an integer of 1 to 3 N-aminoalkylpiperazine. Examples of such amines include, but are not limited to, 2-pentadecylimidazoline, N- (2-aminoethyl) piperazine, and mixtures thereof.

Commercial mixtures of amine compounds can also be used beneficially. For example, one method for producing alkylene amines is to react an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia to form a complex mixture of alkylene amines in which pairs of nitrogen atoms are linked by an alkylene group. And thus forming compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the corresponding piperazine. Low cost poly (ethyleneamine) compounds having an average of about 5 to 7 nitrogen atoms per molecule are commercially available under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100" and the like. Available.

Further, useful amines of the formula NH ₂ - alkylene O- alkylene _m NH ₂ (III) [wherein, m is from about 3 to 70 preferably has a value of 10 to 35]
And the formula R alkylene O-alkylene _n NH ₂ ] _a (IV) wherein n has a value of about 1 to 40, provided that the sum of all n is about 3 to about 70, preferably about 6 to About 35,
And R is a polyvalent saturated hydrocarbon group of up to 10 carbon atoms, wherein the number of substituents on the R group is represented by the value of "a" which is a number from 3 to 6]. And polyamines. Formula (III) or (I
The alkylene group in either of V) may be straight-chain or branched containing about 2 to 7, preferably about 2 to 4 carbon atoms.

The polyoxyalkylene polyamines, preferably polyoxyalkylene dimines and polyoxyalkylene triamines of the above formulas (III) or (IV) may have an average molecular weight in the range from about 200 to about 4,000, preferably from about 400 to about 2,000. Preferred polyoxyalkylene polyamines have about 20
Includes polyoxyethylene and polyoxypropylene diamine and polyoxypropylene triamine having an average molecular weight in the range of 0 to 2,000. Polyoxyalkylene polyamines are commercially available and are available, for example, from Jefferson Chemical Company, Inc. under the trade designation "Jeffamine D-230, D-400, D-400.
-1000, D-2000, T-403 "and the like.

The amine is treated with an oil solution containing 5-95% by weight of dicarboxylic acid material at 100-200 ° C. until the desired amount of water is removed.
Preferably at 125 to 175 ° C., generally for 1 to 10 hours, for example 2 to
By heating for 6 hours, it is easily reacted with a dicarboxylic acid material such as alkenyl succinic anhydride. Heating is
It is preferably carried out to promote the formation of imides or mixtures of imides and amides, rather than amides and salts. The reaction ratio of the dicarboxylic acid material to the equivalent of the amine and other nucleophilic reactants described herein can vary considerably depending on the reactants and the type of bond formed. Nucleophilic reactants, for example, typically 0.1 equivalent per equivalent of amine.
A dicarboxylic acid moiety content (e.g., grafted maleic anhydride content) of 1 to 1.0, preferably about 0.2 to 0.6, e.g., 0.4 to 0.6 mole is used. For example, to convert a mole of olefin to a mixture of amide and imide, the product formed by reacting enough maleic anhydride to add 1.6 moles of succinic anhydride groups per mole of olefin. Preferably about 0.8 moles of pentamine (having two primary amino groups and 5 equivalents of nitrogen per molecule) are used. That is, preferably, pentamine is present at about 0.4 moles per nitrogen equivalent of the amine. Used in an amount sufficient to provide the succinic anhydride portion of the

Tris (hydroxymethyl) aminomethane (THAM) can be reacted with the above acid materials to form amide, imide or ester type additives as taught in British Patent No. 984,409 or, for example, US Pat. 4,102,798
And oxazoline compounds and borated oxazoline compounds as described in US Pat. Nos. 4,116,876 and 4,113,639.

The ashless dispersant may be an ester derived from the above-mentioned long-chain hydrocarbon-substituted dicarboxylic acid substance and a hydroxy compound such as monohydric and polyhydric alcohols or an aromatic compound such as phenol and naphthol. Polyhydric alcohols are the most preferred hydroxy compounds,
And preferably contains 2 to about 10 hydroxy groups,
For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and other alkylene glycols where the alkylene group contains 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, glycerol monooleate, glycerol monostearate, glycerol monomethyl ether, pentaerythritol, dipentaerythritol and the like.

Ester dispersants can also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexane-3-ol and oleyl alcohol. Yet another group of alcohols that can form the esters of the present invention are, for example, oxyalkylene-, oxyarylene-, aminoalkylene- and aminoarylene having one or more oxyalkylene, aminoalkylene or aminoaryleneoxyarylene groups. It includes ether alcohols and amino alcohols, including substituted alcohols.
These include Cellosolve, Carbitol, N, N, N ', N'-tetrahydroxytrimethylenediamine, and oxyalkylene groups where the alkyl group contains from 1 to about 8 carbon atoms. Exemplified by ether alcohols having up to about 150.

The ester dispersant may be a diester or acidic ester of succinic acid, ie, a partially esterified succinic acid, and a partially esterified polyhydric alcohol or phenol, ie, an ester having a free alcohol or phenolic hydroxyl group. Similarly, mixtures of the above exemplified esters are also contemplated within the scope of the present invention.

Ester dispersants can be prepared by one of several known methods, for example, as illustrated in US Pat. No. 3,381,022. Further, the ester dispersant can be subjected to boron treatment in the same manner as the nitrogen-containing dispersant described above.

Examples of the hydroxyamine capable of forming a dispersant by reacting with the above long-chain hydrocarbon-substituted dicarboxylic acid substance include 2-amino-1-butanol and 2-amino-2-amine.
Methyl-1-propanol, p- (β-hydroxyethyl) aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,
3-propanediol, 2-amino-2-ethyl-1,3-
Propanediol, N- (β-hydroxypropyl)-
N '-(β-aminoethyl) piperazine, tris (hydroxymethyl) aminomethane (also known as trismethylolaminomethane), 2-amino-1-butanol-ethanolamine, β- (β-hydroxyethoxy) ethylamine and the like Can be mentioned. Mixtures of these or similar amines can also be used. The above description of nucleophilic reactants suitable for reaction with hydrocarbyl-substituted dicarboxylic acids or anhydrides includes amines, alcohols, and compounds having hybrid amine and hydroxy-containing reactive functionalities, ie, amino alcohols.

A preferred group of ashless dispersants are succinic anhydride groups substituted and polyethyleneamines such as tetraethylenepentamine, pentaethylenehexamine, polyoxyethylene and polyoxypropyleneamines such as polyoxypropylenediamine, trismethylolaminomethane and pentaerythritol As well as those derived from polyisobutylene reacted with these combinations.
One particularly preferred dispersant combination is disclosed in US Pat.
No. 804,763, (A) polyisobutylene substituted with a succinic anhydride group, (B) a hydroxy compound reacted therewith, such as pentaerythritol, and (C) a polyoxyalkylene polyamine such as a polyoxypropylene. A combination of a diamine and (D) a polyalkylene polyamine such as polyethylenediamine and tetraethylenepentamine, wherein (A) is about 0.3 to about 2 moles and (C) is about 0.3 to about 2 moles per mole, respectively. About 0.3 to about 2 moles are used. Another preferred dispersant combination is disclosed in US Pat.
As described in U.S. Pat. No. 2,511, (A) polyisobutenyl succinic anhydride and (B) polyalkylene polyamine such as tetraethylene pentamine and (C) polyhydric alcohol or polyhydroxy substituted aliphatic primary amine such as pentane Includes combinations with erythritol or trismethylolaminomethane.

A (ii) Dispersants in which a nitrogen-containing polyamine is directly bonded to a long-chain aliphatic hydrocarbon as taught in US Pat. Nos. 3,275,554 and 3,565,804 are also useful in the present invention as ashless nitrogen-containing dispersions. In this case, the halogen groups of the halogenated hydrocarbon are replaced by various alkylene polyamines.

A (iii) Another group of nitrogen-containing dispersions that can be used in the present invention are those that contain a Mannich base or Mannich condensation product as known in the art. Such Mannich condensation products are generally described, for example, in U.S. Patent Nos. 3,442,808, 3,649,229 and
As disclosed in US Pat. No. 798,165, about 1 mole of high molecular weight hydrocarbyl-substituted mono- or polyhydroxybenzene (e.g., having a number average molecular weight of 1,000 or more) from about 1 to 2.5 moles of formaldehyde or paraformaldehyde and about 1 mole
It is prepared by condensing with 0.5 to 2 moles of a polyalkylene polyamine. Such Mannich condensation products may include long chain high molecular weight hydrocarbons on the phenolic group, or compounds containing such hydrocarbons, such as polyalkenyl succinic anhydride, as shown in U.S. Pat. Can also be reacted.

Ashless dispersants should not contain boron substituents to provide a fully formulated oily composition that is substantially free of boron.

Component B-Friction Modifier The lubricating oil friction modifier used in the present invention comprises at least one carboxylic acid having a total number of carbon atoms of from 24 to 90 and at least 2 such as 2 to 3 carboxylic acid groups per molecule. Of the alcohol ester or hydroxyamide derivative of the formula (1) in an amount effective for friction adjustment. These ester friction modifiers are generally derived from esterifying a polycarboxylic acid with a dihydric or trihydric alcohol (eg, glycol, glycerol, oxaalkanediol). Therefore, such esters have been used in lubricating oils as friction modifiers, and their preparation and structure have been described in U.S. Pat.
Nos. 4,617,026 and 4,683,069. Such hydroxyamide derivatives of polycarboxylic acids can be used to prepare nucleic acids at elevated temperatures (e.g., ethanolamine, diethanolamine, propanolamine, 3-amino-1, Alkanolamines such as 1-propanediol or amino alcohols).

The carboxylic acid may be an aliphatic saturated or unsaturated acid, and generally has a total carbon number of about 24 to 90, preferably about 24 to 60, and at least 2 such as about 2 to 3, preferably about 2 to 3 carbon atoms. And contains at least about 9 carbon atoms, preferably about 12 to 42, especially 16 to 22, carbon atoms between the carboxylic acid groups. Examples of hydroxyamide friction modifiers have the formula Wherein J ¹ is a carbonized dimer carboxylic acid having a total carbon number of from about 24 to about 90 and containing from about 9 to about 42 carbon atoms between the carboxylic acid groups. A hydrogen group or a skeleton, wherein Z is (a) a hydroxy-substituted alkyl group having from about 1 to about 20 carbon atoms or (b) Wherein A and E are each an alkyl or hydrogen of 1 to 2 carbon atoms, and n ₅ is an integer of 1 to 50, and n ₂ is 0 or 1. n ₃ is 1 or 2 and N ₄ is 1 or 2].

Preferred friction modifiers have the formula HO-J'-OOC-J-COOH (VII) and HO-J'-OOC-J-COOJ "-OH (VIII) wherein J is a hydrocarbon group of an acid. And J 'and J "are either hydrocarbon groups of alkanediols or oxyalkylene groups from oxaalkanediols, as defined below]. Generally about 1 to 3 moles of glycol, preferably 1 to 2 moles, of glycol are used per mole of acid to provide either full or partial esters.

Esters can also be obtained by esterifying a dicarboxylic acid or a mixture of such acids with a mixture of diols, where J is a hydrocarbon group of a dicarboxylic acid and J 'and J "are related to the diol. Hydrocarbon group.

Friction modifiers are typically used in lubricating oil compositions in an amount of about 0.0005-2, preferably about 0.001-0.25, and most preferably about 0.005-0.1% by weight.

Particularly preferred friction modifiers are dimer acid esters. "Dimer acid" herein (which, typically about 85% to 90% of oleic acid or containing linoleic acid) tall oil fatty acid Diels-Alder-mentioned C ₁₈ -C ₂₂ unsaturated fatty acids Used to represent a substituted cyclohexenedicarboxylic acid as obtained by a type reaction, which is a thermal condensation. Such dimer acids typically contain about 36 carbon atoms. The structure of dimer acid can be generalized as follows.

Here, depending on the method by which the condensation of the carboxylic acid was performed
Two of R ² to R ⁵ are two is and the other carboxyl group is a hydrocarbon group. Carboxyl group - (CH _{2) 8
COOH, -CH = CH (CH 2} ) 8 COOH, - (CH 2) 7 COOH, -CH 2
_{-CH = CH (CH 2) 7} COOH, may be _{-CH = CH (CH 2) 7} COOH, and hydrocarbon end groups are _{CH 3 (CH 2) 4 -} , CH 3 (C
_{H 2) 5 -, CH 3} (CH 2) 7 -, CH 3 (CH 2) 4 CH = CH-, CH 3
(CH ₂ ) ₄ CH = CHCH ₂ − and the like. A preferred specific example of a dimer of linoleic acid has the formula: Can be represented by

Also, as used herein, the term "dimer acid" refers to a trimer (and higher homologues) such as about 24% by weight.
Includes compounds containing up to, but more typically about 0% by weight of trimer. This is because, as is well known in the art, the dimerization reaction provides a trimer acid-containing compound having a molecular weight of about three times the molecular weight of the starting fatty acid.

The polycarboxylic or dimer acids described above are esterified with glycols, which are of the formula HO (R ⁶
CHCH ₂ O) x ¹ H (wherein, R ⁶ is and x ¹ is H or CH ₃ is an alkane diol or oxa-alkane diol represented by about 1 to 100 preferably from 1 to 25),
And ethylene glycol and diethylene glycol are particularly preferred. A preferred embodiment is to form the ester using about 1-2 moles of glycol per mole of dimer acid or polycarboxylic acid, such as the ester of diethylene glycol and linoleic acid dimer. Examples of such esters are of the formula (XI) [Where D is And x 'is as defined above].

The preparation of the above-described glycolic acid polycarboxylates and their use as friction reducing esters (i.e., friction modifiers) are disclosed in U.S. Patent No. 4,505,829, which may be referred to if necessary.

Component C-Copper Antioxidants Antioxidants useful in the present invention include oil-soluble copper compounds. The copper antioxidant dissolved in the present invention is non-overbased, ie, the selected compound is not overbased with carbon dioxide under conditions sufficient to form a copper metal carbonate containing compound or complex. Therefore, the copper antioxidant has a total base number (ASTM D2 less than 50 and most preferably less than 20).
896).

Copper can be incorporated into the oil as any suitable oil-soluble copper compound. By "oil-soluble" it is meant that the compound is oil-soluble in the oil or additive package under normal mixing conditions. The copper compound may be in the form of cuprous or cupric. Copper may be in the form of copper dihydrocarbylthio- or dithiophosphate. For the antiwear compound, zinc can be used instead of copper, and in the reactions described below, one mole of cuprous or cupric oxide can be reacted with one or two moles of dithiophosphoric acid, respectively. it can.

Also, the general formula (R ³¹ R ³² NCSS) _m Cu (where n is 1 or 2 and R ³¹ and R ³² are 1 to 18, preferably 2 to
The same or different hydrocarbyl groups containing 12 carbon atoms, examples of which include groups such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic groups). It is also useful. Particularly preferred as R ³¹ and R ³² groups are alkyl groups having 2 to 8 carbon atoms. Thus, the group may be, for example, ethyl, n-propyl, i
-Propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n
-Octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, ticlohexyl, methylcyclopentyl, propenyl, butenyl and the like. To obtain oil solubility, the total number of carbon atoms (ie, R ³¹ and R ³² ) is generally about 5 or more. Also, copper sulfonate, phenate and acetylacetonate can be used. The copper carboxylate compound can be added in the form of cuprous or cupric, and the carboxylic acid moiety has the formula R ⁷ —CO ₂ H (XII) HO ₂ CR ⁸ CO ₂ H (XIII) R ⁷ is selected from the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl, and R ⁸ is selected from the group consisting of alkylene, alkenylene, arylene, alkarylene, and aralkylene. It may consist of a copper monocarboxylate or a polycarboxylate such as derived from a polycarboxylic acid such as a dicarboxylic acid. Generally, the acids of formulas (XII) and (XIII) have at least about 6 to about 35 carbon atoms, preferably about 12 to about 24 carbon atoms, and more preferably about 18 carbon atoms.
Has up to 20 carbon atoms.

Examples of alkyl R ⁷ groups are 5-34 carbon atoms, preferably
Alkyl having 11 to 23 carbon atoms and a branched or straight chain group such as heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-methylhexyl, 3,5 -Ethyl octyl, polybutylene, polypropylene and the like. When R ⁷ is aryl, the aryl group generally contains from about 6 to 20 carbon atoms, such as phenyl, naphthyl and the like. When R ⁷ is alkaryl, each of the above aryl groups can be substituted by an alkyl group, which can be straight-chain, and the total number of carbon atoms in such alkaryl groups is Generally about 7-34, preferably 11-23. Examples of such alkaryl _{groups, -Ar (CH 3), -} Ar (C 2 H 5), - A
r (C ₉ H ₁₉ ), -Ar (C ₄ H ₉ ) ₂ , -Ar (CH ₃ ) ₂ , -Ar (C
₁₀ H ₂₁ ) and the like (where “Ar” is a phenyl ring). When R ⁷ is alkenyl, the alkenyl group generally contains 5-34 carbon atoms, for example hexenyl,
Heptenyl, octenyl, dodecenyl, octadecenyl and the like. When R ⁷ is an aralkyl, the alkyl group (which may be branched or straight chain) may contain 1 to 28 carbon atoms, and such those described above (e.g. phenyl) 1 It can be substituted by up to 3 (e.g. 1 or 2) aryl groups. Examples of such aralkyl _{groups, ArCH 2 -, ArC 2 H} 4 -, ArC 8 H 16 -, Ar
C ₉ H ₁₈ -, and the like _{-, CH 3 CH (Ar)} C 6 H 12. When R ⁷ is cycloalkyl, the cycloalkyl group typically contains from about 3 to 18 carbon atoms and includes, for example, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl,
And cyclododecyl.

Examples of monocarboxylic acids of formula XII are oleic acid, dodecanoic acid, naphthenic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, stearic acid, palmitic acid, myristic acid, lauric acid and the like.

Examples of R ⁸ groups may be straight-chain alkylene having for example 2 to 33 carbon atoms - (wherein, x is an integer of 2 to 33) (CH ₂₎ x- and 4-33 carbon atoms branched alkylene such as -CH ₂ having _{-, - C 2 H 4 -} , - C 3 H 6 -, - C 8 H 16 -,
_{-C 10 H 20 -, - C} 12 H 24 -, - , and the like - C ₁₄ H _28. When R ⁸ is alkenylene, R ⁸ group is generally contain from 4 to 33 carbon atoms, for example _{-CH = C 2 H 3 -,} - CH 2 CH = CHC
₄ H _8- and so on. When R ⁸ is arylene, arylene group generally contains 6 to 20 carbon atoms, such as phenylene, naphthylene and the like. The arylene group is
It may be substituted by an alkyl group containing 1 to 14 carbon atoms. An example of such an alkalylene group is -Ar (CH
_{3) -, - Ar (C} 2 H 5) -, - Ar (CH 3) 2 -, - Ar (C
H ₃ ) ₃ -etc. (Where “Ar” is a phenyl ring). When R ⁸ is aralkylene, an alkylene group as described above can be substituted by one or more (eg, 1-3) aryl groups such as phenyl.

Examples of such dicarboxylic acids are phthalic acid, iso- and terephthalic acid, suberic acid, azelaic acid, sebacic acid,
Decandioic acid, dodecandioic acid, penta-, hepta-, hexa- and octadecanedioic acid. Branched carboxylic acids such as naphthenic acid with a molecular weight of 200 to 500 or synthetic carboxylic acids are also examples.

The carbon atoms of the hydrocarbyl moiety of the acids of formulas XII and XIII are optionally substituted by inert substituents, i.e., substituents that do not interfere with the acid-copper salt formation reaction and do not adversely affect the antioxidant action of the copper carboxylate compound. Can be done. Suitable such inert substituents include halides (eg,
C1, Br), hydroxy, thio, amide, imide, cyano, thiocyano, isothiocyano, keto, carbalkoxy and the like. Preferably, the copper carboxylate is from 8 to
It is derived from an alkanoic or alkenoic monocarboxylic acid containing 35 carbon atoms or a saturated or unsaturated aliphatic dicarboxylic acid containing 8 to 35 carbon atoms. Particularly preferred are copper salts of alkanoic monocarboxylic acids having 12 or more carbon atoms and having 3 or more branches per chain, such as copper octoate, copper oleate and copper dodecanoate. Obtained but examples thereof include such as C ₁₀ -C ₁₈ fatty acid stearic acid or palmitic acid, but is branched carboxylic acids or synthetic carboxylic acids such as naphthenic acids such as unsaturated acids or molecular weight 200 to 500 of oleic acid Preferred because of the improved handleability and solubility of the resulting copper carboxylate.

Alkenyl succinic acid or anhydride copper (Cu ^I and / or C
u ^II) salts are also examples of useful copper compounds. The salt itself,
It can be basic, neutral or acidic. These are (a)
It can be made by reacting the above substances dissolved in an ashless dispersant solution, which have at least one free carboxylic acid (or anhydride) group, with (b) a reactive metal compound. Suitable acid (or anhydride) -reactive metal compounds include those such as cupric or cuprous hydroxides, oxides, acetates, borates, and carbonates or basic copper carbonates .

Examples of the metal salts of the present invention are copper salts of polyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA) and Cu salts of polyisobutenyl succinic acid. Preferably, the metal of choice is its divalent form, eg, Cu ⁺² . A preferred substrate is a polyalkenyl succinic acid wherein the alkenyl groups have a molecular weight greater than about 700. The alkenyl group desirably has an n of from about 900 to 1,400 and up to 2,500, and an n of about 950 is most preferred. Particularly preferred among those described above in the dispersant section is polyisobutylene succinic acid (PIBSA). These materials are desirably dissolved in a solvent such as mineral oil and can be heated in the presence of an aqueous solution (or slurry) of the metal-containing material. Heating can be performed between 70 and about 200 <0> C. Temperatures of 110-140 ° C. are particularly preferred. Depending on the salt formed, it is necessary that the reaction not be left at a temperature above about 140 ° C. for an extended period of time, for example, more than 5 hours, otherwise decomposition of the salt may occur.

Copper compounds useful as antioxidants in the present invention,
It can be manufactured by conventional means. Thus, copper carboxylate can be formed by contacting one or more of the above carboxylic acids with a copper source such as a reactive inorganic or organic copper compound. Preferred copper sources are copper oxide,
Copper acetate, copper hydroxide, copper borate, copper carboxylate and the like.
The acid and copper source are generally contacted for the reaction at a temperature and for a time sufficient to effect the desired reaction in the presence of a solvent or an inert reaction diluent such as water or alcohol. Generally, a period of about 0.5 to 24 hours and a temperature of about 25 to 150 ° C. are suitable, but contact times and temperatures outside these ranges can be used if desired.

Although the copper antioxidant may be incorporated into the lubricating oil composition in any effective amount, such an effective amount may be about 5 to 500 (preferably 10 to 500) copper added to the lubricating oil composition based on its weight. 200 more preferably 10-180 and most preferably 20-
It is contemplated to be sufficient to provide a copper antioxidant amount of 130 (eg, 90-120) ppm. The amount of copper antioxidant within this range is from 0 to about 0.6: 1, preferably less than about 0.4: 1, and most preferably less than about 0.2: 1.
It should be at least sufficient to provide the B: Cu atomic ratio. Of course, the preferred amount will depend on the amount of lubricating oil-based feedstock, among other factors.

The copper antioxidants used in the present invention are inexpensive and effective at low concentrations and do not substantially increase product cost. The results obtained are often better than those obtained with previously used antioxidants which are expensive and used at high concentrations. Copper compounds can be used to replace some or all of the required amount of supplemental antioxidant. Thus, for particularly harsh conditions, it may be desirable to include a supplementary conventional antioxidant.
However, the required amount of supplemental antioxidant is small, much lower than that required in the absence of copper compounds.

Copper carboxylate can be formed by conventional means, such as by contacting one or more of the above carboxylic acids with a copper source such as a reactive inorganic or organic copper compound. Preferred copper sources are copper oxide, copper acetate, copper hydroxide, copper borate, copper carboxylate and the like. The acid and copper source are generally contacted for the reaction at a temperature and for a time sufficient to effect the desired reaction in the presence of a solvent or an inert reaction diluent such as water or alcohol. Generally about 0.5
While periods of 2424 hours and temperatures of about 25-150 ° C. are preferred, contact times and temperatures outside these ranges can be used if desired.

Copper antioxidants (eg, Cu oleate, Cu naphthenate)
Is generally used in the final lubricating oil or fuel oil composition in an amount of about 50-500 ppm (weight ratio) of Cu metal.
The amount of copper antioxidant in this range can range from 0 to about 0.6: 1,
Preferably less than about 0.4: 1 and most preferably less than about 0.2: 1
It should be at least sufficient to provide the B: Cu atomic ratio.

Compositions The additive mixtures according to the invention have very good storage stability and friction control when measured in various environments. Accordingly, the additive mixture is used by blending and dissolving in oily materials such as fuel oils and lubricating oils. The boiling point of kerosene, diesel fuel, domestic heating fuel oil, jet fuel, etc. of the additive mixture of the present invention is about 65 to
When used in a normally liquid petroleum fuel such as a 430 ° C middle distillate, typically from about 0.001 to about 0.5, preferably from 0.001 to about 0.1% by weight, based on the total weight of the composition. Additive concentrations (in the fuel oil) are usually used.

The additive mixtures of the present invention have their primary use in lubricating oil compositions that use a base oil in which the additives are dissolved or dispersed. Such base oils may be of natural or synthetic type. Base oils suitable for use in preparing the lubricating oil compositions of the present invention include crankcase lubricating oils for spark ignition and compression ignition internal combustion engines such as automotive and truck engines, marine and railway diesel engines and the like. What is used conventionally is mentioned. It is also commonly used in power transmission fluids such as automatic transmission fluids, tractor fluids, universal tractor fluids, hydraulic fluids, heavy duty hydraulic fluids, power steering fluids, etc. and / or adapted for use as a power transmission fluid. Useful results can also be obtained by using the additive mixture according to the invention in a base oil. Gear lubricating oils, industrial oils, pump oils and other lubricating oil compositions can also benefit from the formulation of the additive mixtures of the present invention.

Thus, the additives of the present invention can be suitably blended into synthetic base oils such as alkyl esters of dicarboxylic acids, polyglycols, alcohols, poly-α-olefins, alkylbenzenes, organic esters of phosphoric acid, polysilicone oils and the like. .

Natural base oils include mineral lubricating oils,
These are based on their source (eg, paraffinic, naphthenic, mixed, paraffinic-naphthenic, etc.) and their production requirements (eg, distillation range, straight run, cracking, hydrofining). , Solvent extraction, etc.).

More specifically, natural lubricating oil-based feedstocks that can be used in the compositions of the present invention are straight mineral lubricating oils or distillates derived from paraffin, naphthene, asphalt or hybrid base oils. Various mixed oils and, if desired, residual oils, especially those from which asphalt components have been removed, can also be used. These oils can be refined by conventional methods using acids, alkalis and / or clays or other chemicals such as aluminum chloride, and / or
It may be an extraction oil produced by solvent extraction with a solvent of a type such as sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene, crotonaldehyde.

Lubricating oil-based feedstocks typically have about 2.5
Conveniently it has a viscosity of from about 12 to preferably about 2.5 to about 9 cst.

Thus, the additive mixture of the present invention, i.e., the boron-free treated ashless dispersant, friction modifier, and copper antioxidant, typically contains the lubricating oil in a majority amount and the additive mixture typically in the absence of the additive mixture. It can be used in a lubricating oil composition containing a small amount which is effective for imparting improved dispersibility, rust prevention and antioxidation as compared with the above. If desired, additional conventional additives selected to meet the specific requirements of the selected type of lubricating oil composition can be included.

The ashless dispersants, friction modifiers, and copper antioxidants used in the present invention are oil-soluble, soluble in oils with the aid of suitable solvents, or stable dispersing substances. As used herein, "oil-soluble", "soluble" or "stable dispersible" means that the substance is soluble, soluble, miscible or suspendable in oil in all proportions Does not necessarily mean However, this means that the additives are soluble or stable dispersible in the oil to an extent sufficient to exert their intended effect, for example in the use environment of the oil. Moreover, the additional incorporation of other additives may also allow for higher levels of incorporation of dispersants, friction modifiers and / or copper antioxidants if desired.

Thus, although the additive mixture of the present invention can be incorporated into the lubricating oil composition in any effective amount, such an effective amount will provide the lubricating oil composition with an active ashless dispersant, a copper carboxylate antioxidant and a friction modifier. The additive mixture of the present invention is typically sufficient to provide an additive amount of about 0.01 to about 10 (e.g., 0.1 to 8), preferably about 0.2 to about 6% by weight based on the weight of the agent. It is contemplated that

Preferably, the additive mixtures of the present invention and their components comprise from about 5 to 500 ppm of an oil-soluble copper antioxidant compound (calculated as Cu metal), from about 0.1 to about 0.5% by weight of a friction modifier compound and about It is used in an amount sufficient to provide a fully formulated lubricating oil composition containing from 1 to 8% by weight of the ashless dispersant and substantially free of boron as described above.

The additives of the present invention can be incorporated into the lubricating oil in any convenient manner. Thus, they can be added directly to the oil by dispersing or dissolving it in the oil at the desired concentration level. Such compounding can take place at room temperature or at elevated temperatures. Alternatively, adding a suitable oil-soluble solvent and base oil to the additive to form a concentrate (eg, "Adpack"), and then blending the concentrate with a lubricating oil base material to obtain a final processed product Can be. Such concentrates typically range from about 3 to about 45, based on the weight of the concentrate, based on the active ingredient (AI).
% By weight, preferably about 10 to about 35% by weight of dispersant A, typically about 0.001 to 0.25% by weight, preferably about 0.005 to 0.1%
Wt% friction modifier B, typically about 0.005 to 1.0 wt%
Preferably about 0.05-0.2% by weight of copper antioxidant C (expressed as ppm by weight of added copper in the concentrate), and typically about 30-90% by weight, preferably about 40-60% by weight of base Contains oil.

Such concentrates typically contain from about 20% to about 80%, preferably from about 25% to about 65%, by weight of the total active additive (i.e., ashless dispersant, friction modifier, copper modifier) based on the weight of the concentrate. Antioxidants and any other added additives described below) and typically about 80-20% by weight, preferably about 60-20% by weight of base oil. If a metal detergent is present, for example,
They are typically present in such concentrates at about 2-45% by weight.
Preferably it is present in an amount of about 2 to 14% by weight.

The lubricating oil base stock for the additives of the present invention is adapted to perform a selected function by incorporating additional additives therein to form a lubricating oil composition (ie, formulation). You.

Representative additional additives typically present in such formulations include viscosity modifiers, corrosion inhibitors, other antioxidants, friction modifiers, defoamers, antiwear additives, rheological additives. Point depressants, detergents, metal rust inhibitors and the like.

The compositions of the present invention can also be used in combination with a viscosity index (VI) improver to form a multi-grade automatic engine lubricating oil. Viscosity modifiers impart high and low temperature capabilities to the lubricating oil and allow it to remain relatively viscous at elevated temperatures and exhibit acceptable viscosity and flow at low temperatures. Is what you do. Viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters. The viscosity modifier can also be derivatized to include other properties or functions, such as imparting dispersibility. These oil-soluble viscosity controlling polymers are generally from 10 ³ to 10 ^6, preferably from 10 ³ to 10 ^{6 as} measured by gel permeation chromatography or osmometry.
⁴ having a number average molecular weight of ~ 16 ⁶ example 20,000～250,000.

Examples of suitable hydrocarbon polymers include C ₂ -C ₃₀ , including α-olefins and internal olefins, such as C ₂ -C ₈ olefins, which may be linear or branched, aliphatic, aromatic, alkyl, (Which may be aromatic or cycloaliphatic) and a copolymer of two or more of these monomers. Sometimes these are copolymers of ethylene and C ₃ -C ₃₀ olefins, particularly preferred are copolymers of ethylene and propylene. Polyisobutylene, C ₆
And higher homo- and copolymers of α-olefins, atactic polypropylene, hydrogenated styrene, styrene and for example isoprene and / or
Other polymers such as copolymers and terpolymers with butadiene and their hydrogenated derivatives can also be used.
The polymer can undergo a molecular weight reduction, for example by kneading, extrusion, oxidation or thermal degradation, and it can be oxidized and can also contain oxygen. Derivatizations such as copolymers of ethylene-propylene copolymers post-grafted with an active monomer such as maleic anhydride, which can be further reacted with alcohols or amines such as alkylene polyamines or hydroxyamines Polymers (see, for example, U.S. Patent Nos. 4,068,0
Nos. 58, 4,146,489 and 4,149,984) are also included.

Preferred hydrocarbon polymer is 15 to 90 wt% ethylene preferably 30 to 80 wt% of ethylene and 10 to 85 wt%, preferably 20 to 70 wt% of one or more C ₃ -C ₂₈ preferably C
₃ -C ₁₈ and more preferably an ethylene copolymer containing a C ₃ -C ₈ alpha-olefins. Although not required, such copolymers preferably have a crystallinity of less than or equal to 25% by weight as measured by X-ray and scanning calorimetry. Most preferred is a copolymer of ethylene and propylene. An example of this is the modified ethylene-propylene copolymer disclosed in U.S. Patent Application No. 72,825, filed July 13,1987. Other α-olefins suitable for use in combination with ethylene and propylene in place of propylene to form a copolymer or in combination with ethylene and propylene to form terpolymers, quaternary polymers, etc. include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like, and 4-methyl 1-pentene, 4-methyl-
Also included are molecular chain α-olefins such as 1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-pentene, 6-methylpentene-1, and the like, and mixtures thereof.

A terpolymer, quaternary polymer, or the like of ethylene, the _C3-28 α-olefin and a non-conjugated diolefin or a mixture of such diolefins can also be used. The amount of non-conjugated diolefin is generally in the range of about 0.5 to 20 mol%, preferably about 1 to about 7 mol%, based on the total amount of ethylene and α-olphin present.

Polyester IV improvers are generally methacrylic acid,
Is a polymer of esters of and polycarboxylic acid - acrylic acid, maleic acid, maleic anhydride, such as ethylenically unsaturated C ₃ -C ₈ monocarboxylic and fumaric acid.

Examples of unsaturated esters that can be used include:
Esters of aliphatic saturated monoalcohols of at least one carbon atom, preferably 12 to 20 carbon atoms, such as decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate,
Examples include decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate and the like, and mixtures thereof.

Examples of other esters, C vinyl alcohol esters such as vinyl acetate ₂ -C ₂₂ fatty acids or monocarboxylic acids (preferably saturated), vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and their And mixtures thereof. Further, a copolymer of a vinyl alcohol ester and an unsaturated acid ester, for example, a copolymer of vinyl acetate and a dialkyl fumarate can also be used.

Esters may be combined with other unsaturated monomers such as olefins, for example, from 0.2 to 5 moles of C ₂ -C per mole of unsaturated ester.
It can be copolymerized with ₂₀ aliphatic or aromatic olefins or can be copolymerized with such olefins per mole of unsaturated acid or anhydride and then esterified. For example, copolymers of styrene and maleic anhydride esterified with alcohols and amines are known, see, for example, US Pat. No. 3,702,300.

A polymerizable unsaturated nitrogen-containing monomer can be grafted to such an ester polymer in order to impart dispersibility to the IV improver, or a monomer such as an ester can be copolymerized. Examples of suitable unsaturated nitrogen-containing monomers include:
Those containing 4 to 20 carbon atoms, for example, p- (β
Amino-substituted olefins such as -diethylaminoethyl) styrene, basic nitrogen-containing heterocyclic compounds having a polymerizable ethylenically unsaturated substituent such as 2-vinyl-5-ethylpyridine, 2-methyl-5-vinylpyridine, Vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 3-methyl-5-vinylpyridine, 4-methyl-2
-Vinylpyridine, 4-ethyl-2-vinylpyridine,
Vinyl pyridines such as 2-butyl-5-vinyl pyridine and vinyl alkyl pyridine are mentioned.

Also suitable are N-vinyllactams such as N-vinylpyrrolidone or N-vinylpiperidone.

Vinylpyrrolidone is preferred, examples of which are N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone,
-Vinyl-5-methylpyrrolidone, N-vinyl-3,3-
Dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone and the like.

Corrosion inhibitors (also known as anti-corrosion agents) reduce the degradation of metal components that the lubricating oil composition contacts. Examples of corrosion inhibitors include phosphorous sulfides and hydrocarbon sulfides with alkaline earth metal oxides or hydroxides, preferably in the presence of an alkylated phenol or alkylphenol thioester and preferably in the presence of carbon dioxide. It is a product obtained by reacting. Phosphosulfurized hydrocarbons, terpenes, heavy petroleum fractions, or C ₂ -C ₆ olefin polymers such as polyisobutylene such suitable hydrocarbon of 5 to 30% by weight of phosphorus sulfides butylene and about 65 range from about 315 ° C. It is manufactured by reacting at a temperature within 1/2 to 15 hours. Neutralization of phosphosulfurized hydrocarbons is described in U.S. Pat.
This can be done in the manner taught in US Pat.

Antioxidants reduce the tendency of mineral oil to deteriorate during use. This degradation can be evidenced by oxidation products such as sludge and varnish-like deposits on the metal surface, and by increased viscosity. Such antioxidants preferably include alkylphenol sulfides having C ₅ -C ₁₂ alkyl side chains and alkaline earth metal salts of thioesters (eg, calcium nonylphenol sulfide, barium-t-octylphenyl sulfide), dioctylphenylamine, Phenyl-α-
Naphthylamine, phosphorylated sulfurized or sulfurized hydrocarbon, and the like can be mentioned.

Friction modifiers serve to impart suitable friction properties to lubricating oil compositions such as automotive transmission fluids.

Representative examples of suitable auxiliary friction modifiers are U.S. Pat.No. 3,933,659, which discloses fatty acid esters and amides, U.S. Pat. U.S. Pat.No. 4,105,571 discloses glycerol esters of dimerized fatty acids, U.S. Pat.No. 3,779,928 discloses alkane sulfonates, U.S. Pat. Alkylene hydrocarbyl succinimide, S-
U.S. Pat. No. 3,852,205 which discloses carboxyalkylene hydrocarbyl succinamic acids and mixtures thereof
U.S. Pat. No. 3,873 which discloses N- (hydroxyalkyl) alkenyl-succinamic acid or succinimide.
U.S. Pat. No. 3,932,290, which discloses the reaction product of a di (lower alkyl) phosphite and an epoxide;
And U.S. Pat. No. 4,028,258 which discloses alkylene oxide adducts of phosphorylated N- (hydroxyalkyl) alkenyl succinimide. Please refer to these documents if necessary. Most preferred friction modifiers are succinate esters of hydrocarbyl-substituted succinic acids or anhydrides and thiobisalkanols or metal salts thereof as described in U.S. Pat. No. 4,344,853.

Rust inhibitor additives useful in the present invention comprise nonionic surfactants such as polyoxyalkylene polyols and their esters. Such rust inhibiting compounds are well known and can be prepared by conventional means. Nonionic surfactants useful as rust inhibitors in the oily compositions of the present invention typically rely on a number of weak stabilizing groups, such as ether crosslinks, for their surface activity. Nonionic rust inhibitors with ether crosslinking are
Organic substrates containing reactive hydrogen can be made by alkoxylation with an excess of lower alkylene oxides (such as ethylene oxide and propylene oxide) until the desired number of alkoxy groups are located in the molecule.

Preferred rust inhibitors are polyoxyalkylene polyols and their derivatives. This group of substances is commercially available from a variety of sources, such as “Pluron from Wyandtte Chemicals Corporation.
ic Polyols "," Polyglycol 112-2 "(a liquid triol derived from ethylene oxide and propylene oxide) available from Dow Chemical Corporation, and" Tergitol "(dodecylphenyl or monophenyl) available from Union Carbide Corporation. Polyethylene glycol ether) and “Uc
on "(polyalkylene glycols and derivatives).
These are but a few examples of suitable commercial products in the improved compositions of the present invention.

Besides the polyols themselves, also suitable are the esters obtained by reacting the polyols with various carboxylic acids. Acids useful in preparing these esters include lauric, stearic, succinic, and alkyl- or alkenyl-substituted succinic acids, where the alkyl- or alkenyl group contains up to about 20 carbon atoms. ).

Preferred polyols are manufactured as block polymers. Thus, a hydroxy-substituted compound to form a hydrophobic base _{^{R 8 - (OH) n 8}} ( where, n ₈ is 1 to 6 and R is mono- or polyhydric alcohols, phenols, residues naphthol Is reacted with propylene oxide. This base is then reacted with ethylene oxide to form a hydrophilic moiety, thus resulting in a molecule having both a hydrophobic and a hydrophilic moiety. The relative dimensions of these portions can be adjusted by adjusting the ratio of each reactant, reaction time, etc., as will be apparent to those skilled in the art. Thus, regardless of the base oil differences and the presence of other additives, the rust inhibitor is characterized by a hydrophobic portion and a hydrophilic portion present in a ratio that makes it suitable for use in any lubricating oil composition. It is within the purview of those skilled in the art to produce a polyol having the resulting molecule.

If higher oil solubility is required in a given lubricating oil composition, increase the hydrophobic moiety and / or
Hydrophilic moieties can be reduced. If greater oil / water emulsion breaking ability is required, the hydrophobic and / or hydrophilic portions can be tailored to achieve this.

Examples of the compound exemplified by R- (OH) n include alkylene polyols such as alkylene glycol, alkylene triol, and alkylene tetrol, for example, ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and the like. Also, aromatic hydroxy compounds such as alkylated monohydric and polyhydric phenols such as heptyl phenol,
Dodecylphenol and the like can also be used.

Other suitable demulsifiers include U.S. Pat.No. 3,098,827
And the esters disclosed in No. 2,674,619.

Liquid polyols and other similar polyols available under the trade name "Pluronic Polyols" from Wyandotte Chemical Corporation are particularly well suited as rust inhibitors. These “Pluronic Polyols”
Formula (XIV) Equivalent to In the above formula, x, y and z is an integer greater than 1, such as -CH ₂ CH ₂ O- groups account for about 10 to about 40 wt% of the total molecular weight glycol. The average molecular weight of the glycol is from about 1,000 to about 5,000. These compounds are
First, propylene oxide is condensed with propylene glycol to form a hydrophobic base. Is produced by producing The condensation product is then treated with ethylene oxide to add hydrophilic moieties at both ends of the molecule. For best results, the ethylene oxide units should make up about 10 to about 40% by weight of the molecule. The molecular weight of the polyol is about 2.500
~ 4,500 and ethylene oxide units are about 1
Compounds which make up from 0 to about 15% by weight are particularly preferred. It has a molecular weight of about 4,000 and about 10% of it (CH ₂ CH
Polyols derived ₂ O) units are particularly good. Further, alkoxylated fatty amines as described in U.S. Patent No. 3,849,501, amide, alcohol, alkoxylated fatty acid derivative according to the sequence C ₉ -C ₁₆ alkyl-substituted phenols (mono - and diheptyl, octyl, nonyl, decyl, (Such as undecyl, dodecyl and tridecylphenol) are also useful.

Pour point depressants reduce the temperature at which a liquid can flow or be injected. Additives Typical of such so as to optimize the beneficial under the low temperature fluidity of the fluid, C ₈ -C ₁₈ dialkyl fumarate / vinyl acetate copolymers, polymethacrylates, and wax naphthalene.

Foam control can be provided by an antifoamant of the polysiloxane type, such as silicone oil and polydimethylsiloxane.

Antiwear additives, as their name implies, reduce the wear of metal parts. Conventional antiwear agents typical are, for example zinc dialkyl dithiophosphate (where the hydrocarbyl groups are the same or different and C ₁ -C ₁₈ (preferably C ₂ -C ₁₂₎ alkyl, alkenyl, aryl Alkaryl, aralkyl and cycloalkyl).

Sulfonic acid,
Alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, naphthenates and other oil-soluble mono-
And metal salts of dicarboxylic acids. Overbased (ie, overbased) metal salts, such as overbased alkaline earth metal sulfonates (especially Ca and Mg salts) are often used as detergents.

The overbased alkaline earth metal sulfonates are typically heated to a mixture containing oil-soluble alkaryl sulfonic acid and excess alkali metal compound higher than required for complete neutralization of the sulfonic acid, and then the desired excess It is made by forming a dispersion of a carbonate complex by reacting excess metal with carbon dioxide to provide basicity. The sulfonic acids are typically obtained by distillation and / or extraction or by alkylating, for example, benzene, toluene, xylene, naphthalene, diphenyl and halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. Obtained by the sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained by the alkylation of aromatic hydrocarbons such as The alkylation is carried out in the presence of a catalyst with an alkylating agent having about 3 to 30 or more carbon atoms, such as haloparaffin,
It can be carried out using an alkylating agent such as a polyolefin such as a polymer from olefins obtainable by paraffin dehydrogenation, for example ethylene, propylene and the like. Alkaryl sulfonates are usually
It contains about 9 to about 70 or more carbon atoms, preferably about 16 to about 50 carbon atoms per alkyl-substituted aromatic moiety.

Alkaline earth metal compounds that can be used in providing the sulfonate by neutralizing these alkaryl sulfonic acids include magnesium, calcium and barium oxides, hydroxides, alkoxides, carbonates, carboxylic acids Salts, sulfides, hydrosulfides, nitrates, borates and ethers. Examples are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. As noted above, the alkaline earth metal compound is used in excess of that required for complete neutralization of the alkaryl sulfonic acid. Generally, the amount is about 10
It is preferred to use at least 125% of the stoichiometric amount of metal required for complete neutralization, although in the range of 0-220%.

The preparation of highly basic alkaline earth metal alkaryl sulfonates is described, for example, in U.S. Pat.
Nos. 088 and 3,150,089, which are generally known, in which overbasing is achieved by hydrolyzing an alkoxide-carbonate complex with an alkaryl sulfonate in a hydrocarbon solvent-diluent oil. It is preferred to use such hydrocarbon solvent-diluent oils. This is because volatile by-products can be easily removed in a carrier suitable for incorporation into the lubricating oil composition, such as Solvent 150N lubricating oil, and the rust inhibitor additive can be left. For purposes of the present invention, preferred alkaline earth sulfonates have a total base number in the range of about 300 to about 400 and are based on the total weight of the additive system dispersed in Solvent 150 neutral oil. A magnesium alkyl aromatic sulfonate having a magnesium sulfonate content in the range of about 25 to about 32% by weight.

Polyvalent metal alkyl salicylates and naphthenate materials are known additives for lubricating oil compositions to improve high temperature performance and prevent carbonaceous material from sticking to the piston (US Pat. No. 2,744,069). It increased pre basicity of the polyvalent metal alkyl salicylates and naphthenates, C ₈ ~
C ₂₆ alkyl salicylates and alkaline earth metal salts such as calcium salts of a mixture of phenate (U.S. Pat. No. 2,74
No. 4,069) or polyvalent metal salts of alkyl salicylic acids obtained by alkylation of phenol followed by phenation, carboxylation and hydrolysis (US Pat.
No. 3,704,315), which can then be converted to overbased salts by commonly known and used techniques. The preliminary basicity of these metal-containing rust inhibitors is:
TBN levels of about 60-150 ° C are beneficial. Useful polyvalent metal salicylate and naphthenate materials include methylene and sulfur cross-linking materials that are readily derived from alkyl-substituted salicylic or naphthenic acids or mixtures of either or both with alkyl-substituted phenols. Basic sulphide salicylates and their preparation are:
It is described in U.S. Pat. No. 3,595,791.

For the purposes of this disclosure, the salicylate / naphthenate rust inhibitor has the general formula HOOC-Ar (OH) R ⁹ -Xy (ArR ⁹ OH) n ₉ (XVI) wherein Ar has 1 to 6 rings An aryl group,
R ⁹ is an alkyl group having about 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms (optimally about 12), and X represents sulfur (—S—) or methylene (—CH ₂ — ) Is cross-linked,
y is a number from 0 to 4 and n ₉ is a number from 0 to 4. Alkaline earth metals of aromatic acids having, especially magnesium, calcium, strontium and barium
Salt.

The preparation of overbased methylene-bridged salicylate phenate salts is based on phenol alkylation followed by phenation, carboxylation, methylene crosslinking with a coupling agent such as an alkylenedihalide, followed by simultaneous carbonation and salt formation. It is easily implemented by conventional techniques.
Overbased calcium salts of methylene-bridged phenol-salicylic acid having a TBN of 60-150 are representative of rust inhibitor additives that are very useful in the present invention.

Metal sulfide phenates can be considered as "phenol sulfide metal salts", and thus the term is prepared by reacting an alkyl phenol sulfide with a sufficient amount of a metal-containing material to impart the desired alkalinity to the metal sulfide phenate. Metal salt (neutral or basic).

Useful sulfurized alkylphenols, regardless of their manner of preparation, contain from about 2 to about 14%, preferably from about 4 to about 12%, by weight of sulfur, based on the weight of the sulfurized alkylphenol.

The sulfurized alkyl phenol is used in an amount sufficient to neutralize the phenol and, if desired, overbasify the product to the desired alkalinity by procedures well known in the art, such as oxides, hydroxides and complexes. And is converted by reacting A neutralization method using a solution in which a metal is dissolved in glycol ether is preferred.

Neutral or standard metal sulfide phenates are such that the ratio of metal to phenol nucleus is about 1: 2. An "overbased" or "basic" metal sulfide phenate is a metal sulfide phenate in which the ratio of metal to phenol is greater than the stoichiometric amount, for example, the basic metal sulfide dodecylphenate is It has a metal content of up to 100% and greater than the metal present in the metal phenate. In this case, the excess metal is produced in an oil-soluble or dispersible form (as by reaction with CO ₂ ).

Therefore, according to a preferred embodiment, the present invention provides
Provided is a crankcase lubricating oil composition that also contains 8,000 ppm of calcium or magnesium.

Although magnesium and / or calcium are generally present as basic or neutral detergents such as sulfonates and phenates, the preferred additives of the present invention are neutral or basic magnesium or calcium sulfonates.
Preferably, the oil contains 500-5,000 ppm of calcium or magnesium. Basic magnesium and calcium sulfonates are preferred.

These compositions of the present invention may also contain other additives, such as those described above, and other metal-containing additives, such as those containing barium and sodium.

Further, the lubricating oil composition of the present invention can also contain a copper lead-containing corrosion inhibitor. Typically, such compounds are thiadiazole polysulfides containing 5 to 50 carbon atoms, their derivatives and their polymers. Preferred materials are derivatives of 1,3,4-thiadiazole, such as those described in U.S. Pat. Nos. 2,719,125, 2,719,126 and 3,087,932. Particularly preferred are:
2,5-Bis (t-octadithio) -1,3,4-thiadiazole compound commercially available as "Amoco 150". Other similar materials suitable are described in U.S. Pat.
No. 236, No. 3,904,537, No. 4,097,387, No. 4,10
No. 7,059, No. 4,136,043, No. 4,188,299 and No.
No. 4,193,882.

Other suitable additives are the thio- and polythiosulfenamides of thiadiazoles, such as those described in GB 1,560,830. When these compounds are included in a lubricating oil composition, they are preferably present in an amount of 0.01 to 10, preferably 0.1 to 5.0% by weight, based on the weight of the composition.

Some of these numerous additives can provide multiple effects, for example, a dispersant and antioxidant. This method is well known and need not be described in further detail here.

When the composition contains these conventional additives, they are typically mixed into the base oil in an amount effective to provide its normal inherent function. Representative effective amounts (as each active ingredient) of such additives in fully formulated oils are exemplified as follows.

When other additives are used, concentrated solutions or dispersions (in the above-described concentrate amounts) of one or more of the dispersants, friction modifier compounds and copper antioxidants used in the mixtures of the present invention. An additive concentrate (hereinafter referred to as an additive package when the concentrate forms an additive mixture) comprising one or more of such other additives is prepared, thereby providing a number of additives. It may be desirable, but not necessary, to be able to add additives to the base oil at the same time to form a lubricating oil composition. Dissolution of the additive concentrate in the lubricating oil can be facilitated by solvents and by mixing with mild heating,
But this is not required. The concentrate or additive package typically contains the various additives in appropriate amounts to provide the desired concentration in the final formulation when the additive package is mixed with a predetermined amount of base lubricating oil. Is prescribed as follows. Thus, a suitable proportion of additives, typically about 2.5
To form an additive package comprising the active ingredient in a combined amount of from about 90% by weight, preferably from about 15% to about 75% by weight, most preferably from about 25% to about 60% by weight, the balance being a base oil. The additive mixture can be added to a small amount of base oil or other compatible solvent along with other desired additives.

In the final formulation, an additive package of typically about 7% by weight can be used and the balance is the base oil.

All of the weight percentages expressed herein are based on the active ingredient (AI) content of the additive and / or the additive package or formulation consisting of the sum of the AI weight of each additive and the weight of the total oil or diluent. Based on the total weight of the thing.

The invention will be better understood by reference to the following examples, which include preferred embodiments. All parts and percentages are by weight unless otherwise indicated.

Example 1 Part A 1.1 succinic anhydride (SA) moieties per polyisobutylene (PIB) molecule, which has an n of about 2,200, SA:
Polyisobutenyl succinic anhydride with PIB ratio (PIBS
A) is a commercially available grade of polyethyleneamine in S150N mineral oil, which is a mixture of polyethyleneamines having an average of about 5 to 7 nitrogen atoms per molecule;
) To form a polyisobutenyl succinimide containing about 0.97% nitrogen by weight.

Part B-Boron Treatment A portion of the dispersant of Part A is reacted with boric acid, then cooled and filtered to a nitrogen content of about 0.97% by weight, about 0.25%.
A boron-treated polyisobutenyl succinimide having a boron content of 50% by weight and an S150N solution (50% AI) containing 50% by weight of unreacted PIB and mineral oil (S150N) were obtained.

Friction modifier consisting of diethylene glycol ester of linoleic acid dimer and selected dispersant from A and B of Example 1 are alkali metal overbased sulfonate detergent, polyisobutylene succinic anhydride (derived from n = 900 polyisobutylene) The following lubricating oil additive package concentrates used with copper antioxidant, zinc dialkyldithiophosphate antiwear additive (ZDDP), nonylphenol sulfide (NPS) auxiliary antioxidant and S100N diluent (if indicated) Was prepared. The weight ratio of dispersant to each of the other components was kept constant in each of the two sets of concentrates (ie, the same ratio was used in concentrates A and B,
And the same ratio was used in concentrates C and D).

A portion of each concentrate was stored at selected temperatures for extended periods of time to assess their storage stability. The data obtained is summarized in Table I.

From the above tests, the combination of the boron-free dispersant with the copper antioxidant and the friction modifier (concentrates B and D) was the same as the boron treatment dispersant with the same antioxidant and friction modifier (formulation It can be seen that they resulted in greatly improved storage stability compared to A and C).

The foregoing has described the principles, preferred embodiments, and modes of operation of the present invention. However, the invention should not be construed as limited to the particular embodiments disclosed. This is because they should be regarded as illustrative rather than limiting. Those skilled in the art will be able to make numerous changes and modifications without departing from the spirit of the invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C10M 163/00 159: 12 129: 72 129: 74 133: 08 133: 54 129: 58 145: 10 149: 22 159 : 20) C10N 10:02 30:04 30:06 30:10 40:08 40:25 (56) References JP-A-62-181397 (JP, A) US Patent 4,105,571 (US, A) US Patent 4,648,822 ( US, A) European publication 241363 (EP, A1)

Claims (10)

(57) [Claims] (A) an oil-soluble nitrogen-containing ashless dispersant,
(B) an oil-soluble friction modifier comprising at least one alcohol ester or hydroxyamide derivative of a polycarboxylic acid, and (C) an oil-soluble copper antioxidant compound,
An oily composition useful as either a fuel oil, a lubricating oil or a power transmission fluid, wherein the oily composition contains 0 to less than 30 ppm (by weight) of boron. 2. A dispersing agent is formed by reacting a C ₂ -C ₁₀ monoolefins olefin polymer and C ₄ -C ₁₀ monounsaturated acid material having a number average molecular weight of (a) 300 to 5,000 a hydrocarbyl substituted C ₄ -C ₁₀ monounsaturated dicarboxylic acid-forming substance, at least 0.8 on average olefin polymer per molecule present in the reaction mixture used to form the acid-forming substance And (b) a nucleophilic reactant selected from the group consisting of amines, amino alcohols and mixtures thereof, and an oil-soluble reaction product of: 2. The oily composition according to claim 1. 3. The oily composition according to claim 2, wherein the nucleophilic reactant is polyethylene polyamine and the oily composition contains less than 20 ppm (by weight) of boron. 4. The oily composition according to claim 1, wherein the oily substance is a power transmission fluid. 5. The composition of claim 5, wherein the friction modifier is present in an amount of 0.0005 to 5% by weight of the composition.
The oily composition according to any one of claims 1 to 4, which is present in an amount of: 6. A friction modifier wherein at least one selected from the group consisting of alcohol esters and hydroxyamide derivatives of polycarboxylic acids having a total carbon number of from 24 to 90 and at least two carboxylic acid groups per molecule. The oily composition according to any one of claims 1 to 5, comprising a kind of substance. 7. The friction modifier of the formula HO-J'-OOC-J-COOH or HO-J'-OOC-J-COOJ "-OH wherein J is a total of 24 to 90 carbon atoms. And 2 per molecule
A hydrocarbon group of an aliphatic saturated or unsaturated polycarboxylic acid having up to 3 carboxylic acid groups and containing at least 9 carbon atoms between the carboxylic acid groups; And J ″ are the same or different and represent a hydrocarbon group of an alkanediol or an oxyalkylene group, respectively]], and at least one partial ester or diester of the same. 8. The method according to claim 1, wherein the oil-soluble copper antioxidant compound is used in an amount of from 5 to 500 ppm (weight ratio) of added copper in the form of an oil-soluble copper compound. Oily composition. 9. The oil-soluble copper antioxidant compound is a copper salt of a C ₁₀ -C ₁₈ fatty acid, a copper salt of a naphthenic acid having a molecular weight of 200-500, and polyisobutenyl succinic anhydride and polyisobutyric acid. Tenylsuccinic acid (where the polyalkenyl group is 70
9. The oily composition according to any one of claims 1 to 8, wherein the oily composition is selected from the group consisting of copper salts (derived from polymers having a number average molecular weight greater than 0). 10. A storage prepared by a process comprising mixing an ashless dispersant, a friction modifier and a copper antioxidant compound with a base oil in an amount sufficient to form a concentrate and under conditions sufficient to form the concentrate. A stable oil additive concentrate, wherein (A) the ashless dispersant is an oil-soluble nitrogen-containing ashless dispersant and is used in an amount such that the ashless dispersant comprises 3 to 45% by weight of the concentrate. (B) the friction modifier is at least one alcohol ester or hydroxyamide derivative of a polycarboxylic acid, and the friction modifier comprises 0.001-0.25% by weight of the concentrate
And (C) the copper antioxidant compound is an oil-soluble copper antioxidant compound, and the concentrate is added to the concentrate in the form of an oil-soluble copper antioxidant compound. 10. The composition according to claim 1, wherein said concentrate contains from 0 to 30 ppm (by weight) of boron and contains less than 0.005 to 1.0% by weight of copper. A storage-stable oil additive concentrate suitable for addition to a major amount of an oily fuel oil, lubricating oil or power transmission fluid to form the oily composition of claim 1.