JPH01163294A - Ashless lubricant composition for internal combustion engine - Google Patents

Abstract

PURPOSE: To obtain the subject composition suitable for diesel engines and capable of suppressing deposition and of reducing fuel oil consumption by blending a respectively specified quantity of ashless dispersant, sulfurized alkyl phenol and specified organo-sulfur compound.

CONSTITUTION: The composition consisting of a major mount of an oil having lubricating viscosity containing, (A) ≥3 wt.% ashless dispersant consisting of a log chain hydrocarbon group substituted mono or dicarboxylic acid(anhydride) compound (B) ≥2 wt.% sulfurized alkylphenol and (C) an organo- sulfur compound of the formula (R⁴ and R⁵ are each a 2-30C alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl; (w), (z) are 1-8), and containing less than 0.01 wt.% total sulfated ash (SASH).

COPYRIGHT: (C)1989,JPO

Description

TECHNICAL FIELD This invention relates to lubricating oils that significantly reduce carbon deposition on engines. More particularly, the present invention relates to ashless lubricating oil compositions that include an ashless dispersant, sulfurized alkylphenols, and an organic sulfur corrosion inhibitor and are particularly suitable for use in diesel engines.

BACKGROUND OF THE INVENTION There is a need in the art for improved lubricating oil compositions that can be used in engines, particularly diesel engines, with minimal engine build-up and at the lowest tv levels.

Among the conventionally used lubricating oil additives, dihydrocarbyl zinc dithiophosphate has multiple functions in motor oil, including antioxidant action, anti-corrosion action for bearings, and extreme pressure and anti-wear protection for valves. It is known that

Early patents describe compositions in which zinc dihydrocarbyl dithiophosphate and polyisoptenyl succinimide are added to lubricating oils along with other additives such as detergents, viscosity index improvers, and rust inhibitors. Such techniques are described in U.S. Patent Nos. &01a,247, U.S. Pat.

Because phosphoric acid is a catalyst poison for catalytic conversion equipment, and zinc itself is a source of sulfate ash, prior art efforts have been to reduce or eliminate such motor oil components such as zinc and phosphorus. . Publications for reducing phosphorus-containing lubricating oil additives include, for example, U.S. Pat.
No. 0, No. 4,330,420 and No. 4.639.32
There is No. 4.

U.S. Pat. describes a lubricating oil obtained by reacting simultaneously with both sulfur and hydrogen sulfide and reacting the resulting reaction intermediate with an additional hydrocarbon. These additives are generally intended for use in conjunction with other known lubricating oil additives, such as overbased metal detergents, polyisoptenyl succinic acid detergents, and phenolic antioxidants. . Although it is stated that the amount of zinc additive can be significantly reduced, resulting in a low-ash to ash-free lubricating composition, this clearly refers to the ash derived from zinc and does not include other ash. It does not refer to the total ash content.

U.S. Pat. No. 4,550,420 discloses a low ash, low phosphorous motor oil having improved oxidative stability by containing synergistic amounts of a dialkyldiphenylamine antioxidant and a sulfurized polyolefin. ing. According to the patent, due to the synergistic action of these two components,
The loss of phosphorus in the form of zinc dithiophosphate is compensated. The complete motor oil composition consists of 2-10% (jl!ff1%, same below) ashless detergent, α5-5% magnesium or calcium detergent salts (an amount to provide at least 11% magnesium or calcium), 15-2.0% zinc dialkyldithiophosphate, α2-2.0% dialkyldiphenolamine antioxidant, 15-4% sulfurized polyolefin antioxidant, 2-10% of the first ethylene pyrene ■ Improver 1: 2nd improver consisting of a methacrylate terpolymer; and the remainder consisting of base oil.

U.S. Pat. No. 4,659,324 states that metal dithiophosphates are useful as antioxidants, but are a source of ash;
reacting an olefinically unsaturated aliphatic hydrocarbon having 8 to 36 carbon atoms simultaneously with both sulfur and at least one fatty acid ester to form an intermediate reaction product;
It then consists of the reaction product obtained by reacting this with additional sulfur and cyclobentadiene dimer or 01-C4 alkyl substituted cyclobentadiene dimer. When using the additives of this patent, the amount of zinc additive is said to be significantly reduced to provide low to ashless lubricant compositions. In this patent, the ash content refers to the content derived from zinc, and does not refer to the total ash content. Conventionally, metal cleaning agents have been used in motor oil to inhibit surface layer formation and corrosion. By minimizing the obstruction or reduction of restricted openings and gaps between movable members, surface corrosion is prevented from adversely affecting the internal combustion engine.

U.S. Pat. A low ash lubricating oil based on mineral oil containing zinc dialkylaryl dithiophosphate is described.

This lubricating oil was manufactured for the purpose of providing a formulated oil that passes the MS-IIC rust test and the L-58 bearing weight loss test. The patent describes a five-part oil composition containing an overbased calcium detergent, ZDDP, trialkanolamine, and optional lubricant additives, which have a viscosity index, l1fft oxidation, and dispersibility. and provides antifoaming properties.

U.S. Pat. No. 4,153,562 relates to an antioxidant particularly useful in combined lubricants suitable for use under severe conditions in low ash automatic crankcase oils, which are phosphorodithioic acid salts of sulfurized alkylphenols. is produced by condensing it with an unsaturated compound such as styrene. Specifically, the antioxidant is α3~t25% (weight%
...) added to the lubricating oil (Example 5), plus about 2.65% polyisoptenyl boride succinimide detergent and about 06% magnesium (overbased magnesium sulfonate). detergent inhibitor) and about 101% zinc dialkyldithiophosphate antiwear agent (
C4/C5 alkyl group).

U.S. Pat. No. 4,157,972 states that the demand for unleaded fuels and ashless lubricating oil compositions necessitated research into non-metallic (ashless) alternatives to metal-organic detergents; Tetrahydropyrimidyl-substituted compounds useful as bases and rust inhibitors are disclosed. An example of that patent compares the performance of various lubricating compositions in the Ford 78 surface test (Table I) and various other lubricating compositions designated as low or ashless in the wet room rust test (Table ■). The amount of total ash (SASH) for the low ash lubricating compositions is not stated and cannot be calculated from the data given for the metal cleaners and ZDDP compounds described therein.

U.S. Pat. No. 4,165,292 teaches that overbased metal compounds provide effective rust protection to automotive crankcase G4 lubricants and that in the absence of overbased additives or as in ashless extraction, It is stated that rust formation becomes a serious problem in the presence of small amounts of this additive, such as in low ash oils. Such rust prevention conditions are evaluated by ASTM Sequence IIC Engine Test. The non-naturally occurring rust inhibitor described in the patent combines an oil-soluble basic organic nitrogen compound (having a specified basicity) with an alkenyl or alkyl substituted succinic acid having 12 to 50 carbon atoms. consists of things. A basic organic nitrogen compound and an organic acid are used in combination to produce the desired antirust effect. It is stated that best results are achieved by using an excess of amine over the amount of amine required to form the neutral salt of the substituted succinic acid.

U.S. Pat. No. 4,502,970 describes lubricants, dispersants,
An improved crankcase lubricating oil composition is described which optionally contains an overbased metal detergent, a zinc dialkyldithiophosphate rust inhibitor, and anhydrous polyisoptenyl succinic acid. Specific examples include 6% (by weight) polyisoptenyl succinimide detergent, polyisoptenyl succinimide anhydride, overbased metal sulfonate or overbased sulfurized phenolic acid detergent. , zinc dialkyldithiophosphate antiwear agent, and base oil.
．． This is a lubricating oil composition containing one of 0%, 10%, 2.0%, 10%, and 9tO%.

European Patent No. 24146 describes lubricating oil compositions containing copper antioxidants, for example 10% of 40
0 TBN magnesium sulfonate (containing 92% magnesium), a, S% of 250 TBN calcium phenolate (containing 95% calcium) and zinc alkyl dithiophosphate (alkyl groups or mixtures thereof having 4 to 5 carbon atoms). , P2S5 is reacted with a mixture of about 65% isobutyl alcohol and 35% amyl alcohol so that phosphorus is contained in the lubricating oil composition at a rate of 10%).

GB 2062672 describes an additive composition comprising a sulfurized alkylphenol and an oil-soluble carboxylic acid dispersant containing hydrocarbon basic groups with a number average molecular weight of at least 1300, which produces an ash content. It is described to be used in combination with cleaning agents.

However, it is extremely difficult to improve the lubricant technology described therein, which was developed for use in gasoline or light diesel engines for passenger cars and light trucks, for use in diesel engines used under harsh conditions. It is very difficult.

R, D, Hereamp rSA E Technical Paper Series, Penomy Black 851720 (1983
) J reported a method for determining the relative ability of various oils to reduce the consumption of each +11 lubricating oil composition in a heavy duty diesel engine. According to the report, when deposits on the top surface of diesel engine pistons were analyzed, they were found to contain organic binding components containing high molecular weight esters. It is estimated that it is a precursor of sexual substances. Improved antioxidants have been shown to be the key to preventing premature consumption of lubricating oils.

A, A, 5ehetelieh rS A E technical is - par series, is - par 4831722 (1
983) J reported the effects of various lubricating oil parameters on the performance of a lubricating oil for heavy-duty diesel engines of the PC-1 type. For over 50 years, sulfated ash (S) has been used in the heavy-duty diesel industry.
ASH) amount from 2.5% (1960) to α8~1%
Correspondingly, the total base number (TBN) D2896 value of heavy-duty diesel engine lubricating oil (hereinafter referred to as heavy-duty oil) has been reduced from 20 or more to 7 to 10, which is the Oshu standard. It's coming. In this way S
The reduction in A S H and TBN is attributed to improved properties of the ashless components (such as ashless day-cell detergents and ashless detergents). In tests using diesel engines, piston deposits or lubricant consumption and 5ASH or T
There is no particular correlation between BN, and 5ASH is about 1-2%.
This is approximately 8 to 17 TBN. In contrast, ash-free content has been found to be well correlated with piston deposits (with 92% confidence) and lubricant consumption (with 98% confidence). According to the same paper, this correlation is described for diesel fuel with an average sulfur content of about 0.5% or less. Ash accumulation is accelerated in hotter engine areas. The same paper found a correlation between the amount of oil vi and piston deposits (particularly deposits on the top surface of the piston) with 97% confidence, and believed that piston deposits increase oil consumption due to the following two phenomena. It is being (1) The deposits reduce the amount of oil that is swept over the piston top surface, thereby reducing the gas charge behind the piston's top ring, thereby leading to increased oil consumption. (2)
Deposits on the top surface of the piston increase abrasion of the piston cylinder lining, which increases oil consumption by migrating oil through the abraded bore into the combustion chamber of the cylinder. Therefore, the paper concludes that it is necessary to reduce the ash content in the lubricating oil to reduce deposits on the top surface of the piston, thereby reducing oil consumption.

This 1983 Seh@t@1ieh paper reports two test lubricants, each with approximately 1% 5ASH and TBN of 10 and 9, containing an overbased metal detergent along with a zinc source. are doing.

J, A, McG**han rS AE A-Par 4831721j pp. 4848-4869 (1984
) K describes the effects of piston top deposits, fuel sulfur, and lubricant viscosity on diesel oil consumption and cylinder bore abrasion or wear in a series of heavy-duty diesel engine tests. Furthermore, this document states that if there is a large amount of adhesion on the top surface of the piston, oil consumption will increase and the abrasion of the cylinder bore will proceed. It is concluded that the following should be given. Also, according to this document, when a lubricating oil containing α01% sulfated ash in combination with Q,2% fuel sulfur was tested in an AVL-MackTZ675 (turbocharged) engine, it was found that: It is said to be a highly effective ashless inhibitor, producing minimal piston top deposits and also having very low oil consumption. Furthermore, Figure 4 of this paper shows that even if the ash content is reduced to 1% or less, the oil consumption in the engine will be 0.01% from 1% to 5ASH.
We are not aware of any beneficial effect on oil consumption when the 1 ash content is reduced below 1%, as it increases as the ash content is reduced to less than 1%. This fact indicates that a low but still significant amount of 5ASH is present in lff1
This leads to the idea that this is required to prevent increased oil consumption as a result of abrasion of the pores causing corrosion. The same literature concludes that deposits on the top surface of the piston are related to oil consumption, but are not directly related to the sulfated ash (5ASH) content of the lubricating oil, and that these deposits do not change the composition of the crankcase oil. It is explained that this can be suppressed by

(Problems with the prior art) The lubricating oil compositions proposed so far cannot sufficiently reduce deposits on the engine and suppress oil consumption to the minimum level in heavy-duty diesel engines. (Objective of the Invention) Therefore, the object of the present invention is to improve the additives of lubricating oil compositions so that deposits can be reduced when used in heavy-duty diesel engines, and at the same time, lubricating oil cleaners can be reduced. v
An object of the present invention is to provide a lubricating oil composition capable of sufficiently reducing the amount of t.

(Summary of the Invention) The present invention comprises oil having a lubricating viscosity as the majority component, and minor components (A) at least one ashless dispersant of 5% or more, and (B) 2% by weight. at least one of the above sulfurized alkylphenols, and (c) o, tmf
f1% or more of at least one of the following formula% (where R4 and R5 are linear or branched alkyl groups having 2 to 30 carbon atoms, cyclic groups, or alicyclic groups, aryl groups, alkylaryl groups, or an arylalkyl group, W and 2 are from 1 to 8), and the amount of total sulfated ash (SASH) is less than (L01 weight percent). , to achieve the above objectives.

The invention also provides that the lubricating oil compositions of the invention are particularly useful for use in heavy duty diesel engines, particularly those powered by low sulfur fuels.
In a diesel engine with at least one gas-tight top piston, which is particularly preferably driven by a fuel oil with a sulfur content of less than 1% by weight,
The metal content is adjusted so that the total sulfated ash (SASH) of the oil is less than α01% by weight, and (A) 5 is added to the oil.
% or more by weight of at least one ashless dispersant; and (B)
Zffi amount % or more of at least one sulfurized alkylphenol; and (C) a copper corrosion inhibiting amount of at least 4 organic sulfur compounds of the following formula (wherein R4 and R5 are straight or branched alkyl having 2 to 50 carbon atoms); group, cyclic group, alicyclic group, aryl group, alkylaryl group, or arylalkyl group, and W and 2 are 1 to 8), and the total sulfated ash content (SASH) is 1 weight of CLO. An improved lubricity method is provided which comprises charging a lubricating oil composition with an adjusted metal content of less than or equal to %.

DETAILED DESCRIPTION OF THE INVENTION Ashless, nitrogen- or ester-containing dispersants suitable for use in the present invention include (1) oil-soluble salts, amides, imides, oxazolines, and esters; A mono- or dicarboxylic acid or its anhydride having a chain hydrocarbon group, (■) an aliphatic hydrocarbon to which a polyamine is directly bonded, and (fil) a long-chain hydrocarbon group I M iff 1 mole of a phenol having about 1 to 2 Mannich condensate obtained by condensation with .5 moles of formaldehyde and about 0.5 to 2 moles of polyalkylene polyamine. In the above five cases, the long chain hydrocarbon group is a 02-C10%, e.g., C2-C5, monoolefin, and its number average molecular weight is about 300 to about 5,000.

A (1) Nitrogen-containing or ester-containing dispersants include oil-soluble salts, amides, imides, oxazolines, and esters;
mixtures thereof, long-chain hydrocarbon group-substituted mono- or dicarboxylic acids or their anhydrides (long-chain hydrocarbon groups are C2-010%
For example, it is a monoolefin of 02 to C5, and its number average molecular weight is about 700 to 5,000.

The long-chain hydrocarbon-substituted mono- or dicarboxylic acid materials used in the dispersant, i.e. acids, anhydrides, or esters, are
On average for each mole of hydrocarbons, especially polyolefins, about 18 to 2.0 mol, preferably 10 to 16 mol, such as 11 to 13 mol, of alpha- or beta-unsaturated C4-10 unsaturated dicarboxylic acids, their anhydrides; or substituted with its ester. Such dicarboxylic acids or their anhydrides or esters include fumaric acid, itaconic acid,
Maleic acid, maleic anhydride, chloromaleic acid 17
These include dimethyl malate, chloromaleic anhydride, acrylic acid, succinic acid, and cinnamic acid.

Preferred olefin polymers for reacting with unsaturated dicarboxylic acids are primarily 02-010% e.g. 02-C5
It is a polymer containing monoolefin.

Such olefins include ethylene, propylene-1-butylene, imbutylene, hanthene, octene-1, styrene, and the like. Polymers include not only homopolymers such as polyisobutylene, but also ethylene-propylene, butylene-
Copolymers such as isobutylene and propylene-isobutylene are also included. Other copolymers include isobutylene-butadiene copolymers, ethylene-propylene-copolymers, etc. in which a small amount of the monomers constituting the copolymer, e.g. 1-10 mol %, are C4-Cta non-conjugated diolefins. 1,4-hexadiene copolymers. In some cases, the olefin polymer may be fully saturated, such as ethylene-propylene copolymers prepared by Ziegler-Natsuta synthesis using hydrogen as a molecular weight modifier.

The olefin used as a dispersant usually has a number average molecular weight of about 700 to about 500°, more preferably about 800 to about 500°.
It is about 3000. Particularly useful polyolefins have number average molecular weights from about 900 to about 2,500 and have about one terminal double bond per molecule. A particularly useful starting material for preparing dispersants is polyisobutylene. There are several methods for determining the number average molecular weight of such polymers.

Among these, the convenient method is gel permeation method (GPC), which, according to Tore K, can even reveal the molecular weight distribution (W, W).

YAU et al. “Modern, size, exclusion.

Chromatography,” John, Wiley, and.

(See Sands, Inc. (1977)).

Olefin polymer with C4-C10 unsaturated dicarboxylic acid 1
Methods for reacting with the anhydride or the ester are known. For example, methods of simply heating olefin polymers and dicarboxylic acids together are described in US Pat. Nos. 5,561,673 and 5,401,118. According to this, a thermal "ene" reaction takes place. Alternatively, first add 60 to 250 halogens (chlorine or bromine) to the olefin polymer.
℃, e.g. 120-160℃ for about 0.5-10 hours, preferably 1-7 hours, to remove about 1 of the olefin polymer.
-8% by weight, preferably 3-7% by weight halogenation, and then the halogenated main body is heated with a sufficient amount of unsaturated acid or acid anhydride at 100-250°C, usually 180-250°C.
The reaction is carried out at a temperature of 5 DEG C. for about .alpha.5 to 10 hours, for example 3 to 8 hours, thereby obtaining a reaction product containing a given number of unsaturated acids per mole of halogen or polymer. This method is described in US Patent No. 5087456.5172B9.
2.3272746 and others.

An alternative method is to mix the olefin polymer and the unsaturated acid material and heat while adding chlorine. This type of method is described in US Pat. No. 5,215,717.5251,587.39
1764.4110549 and 4234435, and British Patent No. 1441219.

The use of halogen typically results in about 65 to 95 weight percent of the polyolefin, such as polyisobutylene, being reacted with the dicarboxylic acid material. When a thermal reaction is carried out without using a halogen or a catalyst, usually only 50 to 75% by weight of polyisobutylene reacts. Chlorine helps improve reactivity.

For convenience, the functional ratio of the dicarboxylic acid-forming substance to the polyolefin (0.8 to 2.0, etc.) is based on all the polyolefins used (total of reacted and unreacted polyolefins).

The dicarboxylic acid-producing substance may be further reacted with amines, alcohols such as polyhydric alcohols, amino alcohols, etc. to form other dispersants.

If the acid-generating substance is further reacted (e.g. neutralized),
Generally more than 50% and up to 100% of the acid moieties will react.

The nucleophilic reactant used to neutralize the hydrocarbon-substituted dicarboxylic group may contain from about 2 to about 60 carbon atoms, preferably 2 carbon atoms per molecule.
Included are mono- and (preferably) polyamines containing about 1-12, preferably 5-12, more preferably 5-9 nitrogen atoms. These amines may be hydrocarbylamines or may be hydrocarbylamines having other groups such as hydroxyl group, alkoxy group, amide group, nitrile group, imidacillin group, etc. Hydroxyamines having 1 to 6 hydroxyl groups, preferably 1 to 5 hydroxyl groups, are particularly useful.

Preferred amines are aliphatic saturated amines, including those of the formula:

Here R, R', R', R"' are hydrogen, C1-C2
5 straight or branched alkyl groups, C1-C12 alkoxy C2-C6 alkylene groups, C2-C12 hydroxyamino alkylene groups, and 01-C12 alkylamino C2
-C6 alkylene group, and R''' may also be a group of the following formula.

Here, R/ is as defined above, 1s11' may be the same or different and is 2 to 6, preferably 2 to 4, *s t' may be the same or different and the total is 15 0-10, preferably 2-7, more preferably 3-7. In order to facilitate the reaction, R, R', R', R"', l such that the compounds of formulas I and (2) above have at least one primary or secondary amine, preferably both.
, s/, t, t' is preferably selected. This means that at least one of RSR', R', and R/# is hydrogen, or when R'' is hydrogen or the group 2 has a secondary amine, t in formula 2 must be 1 or more. The most preferred amines are those of formula 2,
It has one or more primary amine groups and one or more (preferably three or more) secondary amines.

Examples of suitable amines include:

1.2-diaminoethane, L5-diaminopropane, 1
．． 4-diaminobutane, 1,6-') aminohexane,
Polyethyleneamines such as diethylenetriamine, triethylenetetramine, tetraethylene are tamamine, t2-
Polypropyleamine such as propylene acyamine, di(1
,2-propylene)triamine, di(L5-propylene)triamine, N,N-dimethyl-13-diaminopropane, N,N-di(2-aminoethyl)ethylenediamine, N,N-si(hydroxyethyl)-1 ,3--7'
Lopylenediamine, 6-dozosyloxyprobylamine, N-dodecyl-ts-,/romandiamine, trididroxymethylaminoethane (THAM), diisopropanolamine, jetanolamine, triethanolamine, 7-no, Aminomorpholines such as '-s and rjt+)-tacyloamine, N-(s-aminopropyl)morpholine, and mixtures of two or more thereof.

Other useful amine compounds include:

Alicyclic diamines such as 14-di(aminoethyl)cyclohexane, heterocyclic diamines such as imidacillin, and N-aminoalkylpiperazine represented by the following formula (IV).

Here, pl and p2 are integers of 1 to 4 that may be the same or different, and nl, n2, and n3 are integers of 1 to 3 that may be the same or different. Examples of such amines include 2-pentadecyl imidacilline, N-(2-aminoethyl)piperazine, and the like.

Commercially available amine mixtures can advantageously be used. For example, alkylene amines can be produced by reacting alkylene civalide (ethylene dichloride or propylene dichloride) with ammonia to produce a complex mixture of alkylene amines in which nitrogen pairs are bonded by alkylene groups, such as diethylene triamine, triethylene triamine, Tetraethylenepentamine and pi form compounds such as radine isomers. Approximately 5
A low cost polyethylene diamine compound with ~7 nitrogen atoms per molecule is Polyamin H%P
olyamin 400, Dov Polyamin
It is commercially available under trade names such as E-100.

Useful amines include polyoxyalkylene polyamines of the formula:

NH2-alkyl@ne÷0-alkylene→=
NH2(V) where m is about 5 to 70, preferably 10 to
It is 55. Similarly, the following formula is also included.

where n is about 1 to 40, and the sum of all n's is about 5 to 70, preferably about 6 to 55, and R is a polyvalent saturated hydrocarbon group having up to 10 carbon atoms; The number of substituents on the R group is represented by a, which is from 3 to 6. Formula V
The alkylene group in or (2) may be straight or branched having about 2 to 7, preferably about 2 to 4 carbon atoms.

Polyoxyalkylene polyamine 1 of formula V or (2) preferably polyoxyalkylene diamine and polyoxyalkylene triamine have an average molecular weight of about 200 to 4000,
Preferably it may have about 400-2000. Preferred polyoxyalkylene diamines have an average molecular weight of about 200 to
Contains 2000 polyoxyethylene diamine and polyoxyethylene triamine. Polyoxyalkylene polyamines are commercially available, such as J*ffsrmine from Jefferson Chemical Co., USA.
D-250S D-400, D-1000, D-200
It is commercially available under the trade name 0, T-405.

The above amines readily react with certain dicarboxylic acids, such as alkylene succinic anhydride. For example, 5-95% by weight of dicarboxylic acid material is preferably added at about 100-250°C, preferably at 125-120°C until the desired amount of water is removed.
Heat at 75°C for about 1-10 hours, preferably 2-6 hours. It is desirable that the heating be carried out in a manner that favors the formation of an imide or a mixture of imide and amide without the formation of amide and salt. The equivalent (6) ratio of dicarboxylic acid material to amine and other nucleophilic reactants can vary depending on the reactants and the bonds formed. Generally from 0.1 to, preferably from about 12 to α6, such as from 0.4 to 16 moles of dicarboxylic acid moieties (eg, grafted maleic anhydride) may be used per equivalent of nucleophilic reactant, such as amine. for example,
Approximately α8 moles of pentaamine (containing two primary amine groups and 5 equivalents of nitrogen per molecule) are used to add t6 moles of succinic hydrate groups per mole of olefin. Sufficient maleic anhydride is reacted with 1 mole of olefin to convert the resulting product into a mixture of amide and imide. That is, the hantaamine is preferably used at 1 sufficient to provide about (L4 moles (16/α8X5) of succinic acid per nitrogen equivalent of amine.

Nitrogen-containing dispersants are described in U.S. Pat.
It can be further processed by the boration method described in eg No. 254025. This is done by treating a specific acylated ferrous dispersant with a boron compound selected from the group consisting of boron oxide, boron helobenzenate, boric acid, and boric acid esters.
About α1 to 1 nitrogen atom of the above-mentioned acylated nitrogen compound
It can be easily achieved that the number of atoms is approximately 20 atoms. Usually, the dispersant in the invention is about (L
O5~2.0kff1%, e.g. 0.05~0.7j
Contains mli% boron. The boron present in the product as dehydrated boron Mffi combinations (primarily (ano2)s) is believed to be bound to the dispersant imide and diimide as an amine salt such as a diimide metaboronate.

The treatment is about α05-4% by weight, preferably 1-5% by weight.
A boron compound (based on the superposition of the acylated nitrogen compound), preferably boric acid, is added to the acylated nitrogen compound, most commonly in the form of a slurry, with stirring at about 135°C to 190°C. C% e.g. 1-1 at 140-170℃
This can be easily done by heating for 5 hours and then purging with nitrogen at the same temperature range. Alternatively, the boron treatment can be carried out by simply adding boric acid to the hot reaction mixture of the dicarboxylic acid material and amine mixture with removal of water.

Tris(hydroxymethyl)aminomethane (THAM)
reacts with the acid materials described above to form ester-type, amide, or imide additives as shown in British Patent No. 984.409, or US Pat. No. 4,102,798.4116B7.
6 and 4,115,659.

The ashless dispersant may be an ester formed from the long-chain hydrocarbon-substituted dicarboxylic acid material described above and a hydroxy compound such as a monohydric or polyhydric alcohol, an aromatic alcohol such as phenol and naphthol. The polyhydric alcohol is most preferably a hydroxy compound containing 2 to 10 hydroxyl groups, such as ethylene glycol 1 diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, etc.
Other fullkylene glycols have alkyl groups containing about 8 carbon atoms. Other useful polyhydric alcohols are glycerol, glycol monooleate, monoethyl ester of glycol monostearate, hantaerythritol, dipentaerythritol, and mixtures thereof.

Ester dispersants include allyl alcohol, cinnamic alcohol, flopardyl alcohol, and 1-cyclohexane.
It may also be derived from unsaturated alcohols such as 5-ol and hyoleyl alcohol.

Alcohols that can produce esters used in the present invention include ether alcohols and hyamino alcohols,
Examples include one or more oxyalkylene groups, aminoalkylene groups, or aminoarylene groups, oxyalkylene substituted alcohols having an oxyarylene group, oxyarylene substituted alcohols, aminoalkylene substituted alcohols, and aminoarylene n-alcohols.

These include, for example, Cellosolve, Calpitol, N*
N tN I , N /-tetrahydroxy-trimethylene diamine, and up to about 150 oxyalkylene groups (each alkylene group containing 1 to about 8 carbon atoms)
Ether alcohol theal.

Ether type dispersants are succinic acid or acid esters (ie partially esterified succinic acid) glue esters, partially esterified polyhydric alcohols or phenols (free alcohols or esters with phenolic hydroxyl groups). Mixtures of the esters exemplified above can also be used.

Ester-type dispersants are made using one of several known methods, such as those shown in US Pat. No. 5,581,022. Ester type dispersants may be borated similarly to nitrogen-containing dispersants.

Hydroxyamines that can react with the long-chain hydrocarbon-substituted dicarboxylic acid materials described above to form dispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p-( beta-hydroxyethyl)-aniline, 2-7mi/-1-furopanol, 3-amino-1-
Propanediol, 2-amino-2-methyl-1,5-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(beta-hydroxypropyl),
-N/-(beta-aminoethyl)-pi is radine, tris(hydroxymethyl)aminomethane (also called trismethylolaminoethane), 2-amino-1-butanol, ethanolamine, beta(betahydroxyethoxy)ethylamine, etc. included. Mixtures of these or similar amines can also be used.

Nucleophilic reactants suitable for reacting with hydrocarbon-substituted dicarboxylic acids or their anhydrides include amines, alcohols,
Included are mixed amine compounds (eg, compounds with hydroxyl-containing reactive functional groups such as aminoalcohols).

A preferred class of ashless dispersants includes substitution with succinic anhydride;
and polypropylene reacted with one or more of polyethylene amines (eg, tetraethylene amine, antaethylene hexamine), polyoxyethylene and polypropylene amines (eg, polyoxypropylene diamine), trimethylolaminoethane, and antaerythritol. Preferred combinations include (1) polyisobutyne substituted with a succinic acid group, (1) a hydroxy compound such as hantaerythritol, (iii) a polyoxyalkylene diamine such as polyoxypropylene diamine, (IV
) Polyethylene diamine and tetraethylene are reacted with tamamine, and as described in US Pat. No. 5,804,765, (II
), (Ill ) and (lv) respectively about [lL3~
Use 2 moles. Other preferred combinations include (1) polyisobutylsuccinic anhydride as described in U.S. Pat. or in combination with a polyhydric alcohol-substituted aliphatic primary amine (eg metaerythritol or tristyrolaminoethane).

A (1) Other materials useful as ashless nitrogen-containing dispersants are those in which nitrogen-containing polyamines are directly bonded to long-chain aliphatic hydrocarbons, and those in which the halogen groups of halogenated hydrocarbons are replaced with various alkylene polyamines. Obtained by substitution. These dispersants are described in U.S. Pat.
No. 55804.

A (fil) Other materials useful as ashless nitrogen-containing dispersants include the well-known Mannech bases or Mannech metal complexes. Such Mannich condensates generally contain about 1 mole of high molecular weight hydrocarbon groups M
Dust mono- or polyhydroxybenzene (number average molecule [1
000 or more) with about 1 to 2.5 moles of formaldehyde or paraformaldehyde and about 0-5 to 2 moles of polyalkylene polyamide.

This method is described, for example, in US Pat. Nos. 5,649,229 and 3
No. 798165. Such Mannich condensates may contain long chain high molecular weight hydrocarbons on the phenolic group, or may contain such hydrocarbons (e.g., polyalkenylsuccinic anhydrides shown in U.S. Pat. No. 3,442,808). It may also be reacted with a compound.

Component B (at least one sulfurized alkylphenol) Component-B in the composition of the invention is at least 1@1 sulfurized alkylphenol as an antioxidant. Sulfurized alkylphenols and their production methods are well known,
For example, US Pat. No. 2,159,766, US Pat.
No. 2250542, No. 2836565, No. 32
No. 85854, No. 5538166 to No. 5844956
No. 3,951,830.

Generally, sulfurized alkylphenols can be prepared by reacting alkylphenols with elemental sulfur, halogenated sulfur (such as -sulfur chloride or sulfur dichloride), mixtures of sulfur halides and sulfur dioxide, and the like. Preferred sulfiding agents are sulfur halides, particularly sulfur chloride, especially sulfur dichloride (SC12).

The alkylphenols sulfurized to produce component B are generally compounds containing at least one hydroxyl group and at least one alkyl group attached to the same aromatic ring. The alkyl group generally contains about 3 to 100 carbon atoms, preferably about 6 to 20 carbon atoms. The alkylphenols contain at least one hydroxyl group (such as resorcinols, hydroquinones and kanafurs) or may contain more than one alkyl group, but they usually contain one of each. Those in which the alkyl group and the hydroxyl group are in ortho, meta, and para positions with respect to each other, and mixtures thereof, also fall within the scope of the present invention.

Examples of alkylphenols include the following.

n-propylphenol/L/, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, n-dodecylphenol, furoane triple-substituted phenol, octadecylphenol, ercosylphenol , polybutene (average molecular weight of about 1000) substituted phenol, n-dodecylresorcinol, and 2.4-:)-t-7' tylphenol. Also included in this category are alkylphenols crosslinked with methylene groups by reacting alkylphenols with formaldehyde or formaldehyde-generating substances (such as trioxane or paraformaldehyde).

Sulfurized alkylphenols are typically produced by reacting an alkylphenol with a sulfurizing agent at a temperature in the range of about 100-250°C.

The reaction can be carried out in a substantially inert diluent such as toluene, xylene, petroleum naphtha, mineral oil, cellosolve, and the like. When the sulfurizing agent is halogenated sulfur,
Acidic materials such as hydrogen halides can be removed by vacuum stripping the reaction mixture or by purging with an inert gas such as nitrogen, especially if no diluent is used. When the sulfiding agent is sulfur,
Sulfurization products are scavenged with an inert gas such as nitrogen or air to remove sulfur oxides, etc.

This component is a copper corrosion inhibitor and is expressed by the following formula: λ5
-Dimethylcapto L contains at least one polysulfidized hydrocarbon that is a derivative of 3,4-thiadiazole.

Here, R4 and R5 are a linear or branched alkyl ring group, an alicyclic group, an aryl group, an alkylaryl group, or an arylalkyl group, and W and 2 are from 1 to about 8. R4, BS preferably has from 4 to about 16 carbon atoms, more preferably from about 8 to about 14 carbon atoms, and v
Sz is preferably an integer of 1-4.

The polysulfide derivatives of 2,5-dimercapto-1 to 4-thiadiazole described herein can be prepared in several ways. For example, 2.5-:) mercapto- is reacted with 4-thiazole and the appropriate sulfenyl chloride, or dimercaptan is reacted with chlorine and the resulting disulfide chloride is reacted with a primary or tertiary mercaptan. It can be manufactured from TotoK. Bistrisulfide derivatives combine this dimercaptan with mercaptan and sulfur chloride.
:2:2 to 1:2:4 molar ratio of about 50 to 100
Obtained by reacting at ℃. Higher polysulfides can be obtained by reacting thiadiazole di or trisulfides at about 94-310°C. Another method of preparing the polysulfides of the invention is to combine 2,5-dimercap)-tL4-thiadiazole with mercaptan and sulfur in a range of 1:1:1 to 1:4:16.
It can be obtained by reacting at a molar ratio of about 72 to 150°C.

Of the compounds prepared by the above method, preferred are i,! containing from 2 to about 60 carbon atoms! , 4-thiadiazole-2,5-bis(alkyl, di-, tri- or tetra-sulfide) polysulfide. Preferred polysulfides include i,&4-thiadiazole-2.
5-bis(octyldisulfide)-, 4-thiadiazole-2,5-bis(octyltetrasulfide)
, i, 3.4-thiadiazole-2.5-(nonyl disulfide), t3゜4-thiadiazole-2,5-(nonyl trisulfide), 1.3.4-thiadiazole-
2,5-(nonyltetrasulfide), L3=4-thiadiazole-2,5-bis(dodecyldisulfide),
to t4-thiadiazole-λ5-bis(dodecyltrisulfide), i, 14-thiadiazole-2,5-bis(dodecyltrisulfide), 13.4-thiadiazole-245-bis(dodecyltetrasulfide), 2-
lauryldithia-5-thiaalphamethylstyryl-1
, 44-doadiazole, 2-lauryltrithia-5-
Thia alpha methylstylin-1,44-thiadiazole, and mixtures of two or more thereof. Preferred materials are U.S. Pat.
Derivatives of 1,44-thiadiazole as described in No. 7952, particularly preferred are Amo c
.

2,5-bis(t-octadithio)-tt4-thiadiazole and 2,5-bis(nonyldithio)-1,44-thiadiazole (Am
oeo 15 B).

A method for producing component C is further described in U.S. Patent No. 2,719,125.
2719126.3087932 and 44j045,5
It is also listed in the number.

Lubricating oil compositions such as transmission fluids, heavy duty oils suitable for diesel engines (compression ignition type engines) are prepared using the additives of the present invention. The present invention can also be used in a type of crank case lubricant that can be used commonly for gasoline engines and diesel engines. These lubricating oil compositions typically contain several other additives that provide other necessary properties. For example, viscosity index modifiers, ashless antioxidants, ashless corrosion inhibitors, pour point depressants, ashless antiwear agents, etc. can also be used to ensure that the final composition of the present invention satisfies the ashless S A S H condition. used in range.

For preparing heavy-duty lubricating oil compositions, 10 to 80 mff in a hydrocarbon oil (such as mineral oil) or other suitable solvent may be used.
1% (e.g. 20-8 ajnm%) f) It is common to present the additive as a concentrate containing the active ingredient. Such concentrates may contain 3 to 100% of the additive when preparing the final oil composition (e.g. crankcase oil).
It can be diluted with lubricating oil twice as much, preferably 5 to 40 times (heavy ff1).

111 Thick material makes it easier to handle various ingredients,
This is because mixing with lubricating oil becomes easier. Therefore, it is preferable to use component A, the ashless dispersant, mixed with the lubricating oil in an amount of, for example, 40 to 50% by weight.

Component A, BSC, is used by mixing with a base oil consisting of natural, synthetic, or a mixture of both oils having an f4 lubricating viscosity.

Any method can be used to incorporate Component A % BSe into the t-lube oil (base oil). For example, these mixtures can be added directly to lubricating oils by dispersing or dissolving them in the oil with the desired concentration of detergents, inhibitors, antiwear agents, etc. Such incorporation into the additional lubricating oil can be carried out at room temperature or at elevated temperatures.

Alternatively, component ASB, C may be mixed in a suitable oil-soluble solvent and base oil, and the concentrate then mixed with additional base oil to form the final product. Such concentrates typically contain from about 10 to about 70 wt.%, preferably from about 30 to about 60 wt.% of component A, and from about 10 to 40 wt.% of active ingredient (A%I).
% by weight, preferably about 10 to 30% by weight of component B, about 6 to 5% by weight of component C, preferably about 30 to about 80 ffi%, preferably about Approximately 40
~60% by weight base oil (based on total weight of concentrate).

The compositions of the present invention are ashless, i.e. total sulfate ash (5A
SH) is α01% or less, preferably zero. where 5ASH is the weight percent of total ash (corresponding to the metal content of the oil) as determined for a particular oil by STMD874.

The lubricant base oil for component ASB, C can be made into I4 by adding additional additives. #It is suitable for producing a predetermined lubrication effect by forming an oil composition.

Natural oils include animal oils and vegetable oils (castor oil, lard oil'5)
, liquid natural petroleum oils, and mineral lubricating oils such as hydrogen essential oils, solvent-treated or acid-treated paraffinic oils, naphthenic oils, and mixtures thereof. Oils of lubricating viscosity derived from coal and sierre also make useful base oils.

Among alkylene oxide polymers, intermediates thereof, and derivatives thereof, those whose terminal hydroxyl groups have been modified by esterification, etherification, etc. are other known synthetic lubricating oils. Examples of these include: Polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide 1 Alkyl or aryl esters of these polyoxyalkylene polymers (methyl-polyisopropylene glycol ether with an average molecular weight of 1
000, diphenyl ether of polyethylene glycol with an average molecular f of 1500 and 1000, an average molecular f
f11000 N5000 polypropylene glyfur diethyl ether), and their heptano and polycarboxylic acid esters (e.g. tetraethylene glyfur acetate ester, 03-C8 fatty acid mixed esters, and CL5 oxo acid diester). Other suitable synthetic lubricants include: dicarboxylic acids (e.g. phthalic acid, succinic acid, pulkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, speric acid,
Sebacic acid, fumaric acid, adipine iJE, 9-monoyl acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid) and alcohols (e.g. haftyl alcohol, 1hexyl alcohol, dotesyl alcohol, 2-ethylhexyl alcohol, ethylene Glyfur, diethylene glycol heptanoether, diethylene pyrene glycol) esters. Among these, specific esters include diptyl adipate and di(2-ethylenehexyl sebacate).
, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, diaicosyl sepacate,
There are didecyl phthalate, 2-ethylhexyl ester of linoleic acid dimer, and a complex ester that is the 1:2:2 reaction product of heptabasic acid/tetraethylene glycol/2-ethylenehexanoic acid.

Other esters useful as synthetic oils include esters of C5-C12 monocarboxylic acids with polyols and polyol esters such as neopentyl glycol, trimethylolpropane, hantaerythritol, dipentaerythritol, and trihantaerythritol. It will be done.

silicone-based oils, e.g. polyalkylene-,
Polyaryl-, polyalkoxy-1 or polyaryloxysiloxane oils and siliconized oils constitute other useful synthetic lubricating oils. These are nato2ethylsilicute,
Nato-2 isopropyne silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-6th-butylphenyl) silicate, hexa-(4-methyl-2-ethylhexyl) silicate ) disiloxane, poly(methyl)siloxane,
and poly(methylphenyl)siloxane. Other synthetic lubricating oils include esters of phosphorous acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decyl phosphate, etc.) and tetrahydrofuran polymers.

Unrefined, refined, and rerefined oils can also be used in the present invention.

Unrefined oils can be used as is. For example, sierre oil obtained from retorting, petroleum oil obtained from distillation, or ester oil obtained from an esterification process may be used as is.

Refined oils are similar to unrefined oils except that they have modified one or more properties. Purification techniques such as distillation, solvent extraction, acid or base extraction, filtration, percolation, etc. are well known.

Re-refined oil is oil that has been used once and has been refined using the above-mentioned refining method. This type of oil is also called recycled oil or reprocessed oil, and used additives and substances decomposed by the oil may be removed.

The novel lubricating oil compositions of the present invention can be used as multi-grade diesel engine lubricating oil compositions by combining with viscosity index (VSI) modifiers. Viscosity modifiers provide lubricating oils with high or low temperature durability, relatively high viscosity even at cylinder temperatures, and acceptable flow viscosity even at low temperatures. The viscosity modifier may also have other functions, such as imparting dispersibility.

These oil-soluble viscosity modifiers have a number average molecular weight of 105 to 1
06, preferably 104-106, e.g. 2Q, 000
~25 to 000 polymers. This molecular weight is gel f#
It can be determined using permeation chromatography, etc.

Suitable hydrocarbon polymers include two or more C2-C5Os.
Preferably, it contains a single monomer or a copolymer of two or more monomers of C2 to C8 olefins (both alpha olefins and internal olefins). In this case, the olefin is linear,
It can be branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, and the like.

Often these are copolymers of C5-CSa olefins and ethylene, particularly preferably ethylene-propylene copolymers. Other polymers include polyisobutylene, homopolymers or copolymers of 06 or higher alpha olefins, atactic polypropylene, hydrogenated polymers, binary or ternary copolymers of styrene with isoprene or/and butadiene, etc. Styrene copolymers, hydrogenated polymers thereof, etc. can be used. The polymer may be reduced in molecular weight by mastication, extrusion, oxidation, or pyrolysis, and may contain oxygen by oxidation. Further included are post-grafted intermediate polymers of ethylene-propylene and active monomers such as maleic acid, which are further reacted with alcohols or amines (eg, alkylene polyamines, droxyamines, etc.). These are U.S. Patent No. 4089794.4160759 and
It is stated in the number etc. Alternatively, ethylene-propylene copolymers reacted or grafted with nitrogen compounds can also be used. This is described in US Pat. No. 4,068,056.
406805B, 4146489, and 414998
It is stated in No. 4.

Preferred hydrocarbon polymers include 15 to 90% by weight ethylene, preferably 30 to 80% by weight, and 10 to 85% by weight ethylene.
%, preferably 20-70% by weight of 1 or more 05-C2
8, preferably C3 to C18, more preferably C3 to
Contains C8 alpha olefin and copolymers. Although not essential, it is desirable that these copolymers have a crystallinity of 25% by weight or less as measured by X-ray or differential scanning differential thermometry.

Ethylene-propylene copolymers are most preferred.

Other alpha olefins that are suitable for use in place of propylene to make copolymers or that can be used with ethylene and propylene to form terpolymers and quaternary polymers include 1- Butene, 1-hexene, 1-heptene, 1-octene,
1-Nonene, 1-decene, etc. 1-or 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-
Branched alpha olefins such as 1,4,4-dimethyl-1-benthene and 6-methylhebutene-1, and mixtures of two or more thereof are included.

Terpolymers, quaternary copolymers of ethylene, the 05-02B alpha olefins mentioned above, non-conjugated diolefins, mixtures of non-conjugated diolefins, etc. can also be used. Non-conjugated diolefins generally vary from about 0.5 to 20 mole percent, preferably from about 1 to about 7 mole percent (based on the total amount of ethylene and alpha olefins present).

Polyester viscosity modifiers are generally ethylenically unsaturated phase C3
- Polymers of esters of C8 mono- and di-carboxylic acids (methacrylic acid, acrylic acid, maleic acid, maleic anhydride, fumaric acid, etc.).

Examples of unsaturated esters that can be used include esters of aliphatic saturated alcohols containing one or more carbon atoms, preferably 12 to 20 carbon atoms, such as decyl acrylate-F1 lauryl acrylate, stearyl acrylate, Included are fusanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and mixtures thereof.

Other esters include vinyl alcohol esters of 02-C22 fatty acids or monocarboxylic acids, such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, etc., and mixtures thereof. .

Copolymers of vinyl alcohol esters and unsaturated acid esters, such as vinyl acetate and dialkyl fumarates, can also be used.

These esters may further contain other unsaturated monomers, e.g.
It may be further copolymerized with 2 to 5 moles of C2 to C20 aliphatic or aromatic olefin (based on ester), or it may be esterified to a similarly copolymerized product with an unsaturated acid or acid anhydride. Also good. For example, a method of esterifying a copolymer of styrene and maleic anhydride with an alcohol and an amine is shown in US Pat. No. 5,702,300 and the like.

These ester-type polymers may be graft-polymerized with a polymerizable unsaturated nitrogen-containing monomer, or may be ester-copolymerized, in order to impart dispersibility to the viscosity modifier. Suitable nitrogen-containing monomers contain 4 to 20 carbon atoms. This monomer includes amino-substituted olefins such as p-(beta-diethylaminoethyl)styrene, nitrogen-containing heterocyclic monomers containing polymerizable unsaturated substituents such as vinylpyridine and vinylalkylpyridine, such as 2-vinyl −
5-ethylpyridine, 2-methyl-5-vinyl
2-vinylpyridine, 4-vinylpyridine, 3-vinylpyridine, 5-methyl-5-vinylpyridine, 4-vinylpyridine,
Examples include methyl-2-vinylpyridine, 4-ethyl-2-vinylpyridine, and 2-butyl-1-5-vinylpyridine.

N-vinyl lactams are also suitable, for example N-vinylpyrrolidone or N-vinyl bilydone.

Vinylpyrrolidone is preferably used, for example N-vinylpyrrolidone, N-(1-methylvinyl)pyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpyrrolidone! 15-'
) Methylpyrrolidone, N-vinyl-5-ethylpyrrolidone, etc.

Other antioxidants suitable for use in the present invention are oil-soluble copper compounds. Copper may be mixed into the base oil as any suitable oil-soluble copper compound. Oil-soluble herein means that it dissolves in oil or wheel machining concentrate under normal mixing conditions.

The copper compound may have the form of monovalent or divalent steel. Copper can be used as a copper dihydrocarbyl thio- or dithio-phosphate, with copper replacing the zinc present in the compositions or reactions described above.

In particular, 1 mole of cupric oxide or cupric oxide each has 1
or 2 moles of dithiophosphoric acid. Alternatively, copper may be added as a copper salt of a synthetic or natural carboxylic acid. Such acids include C10-C18 fatty acids (stearic acid, palmitic acid, etc.), but more preferably unsaturated carboxylic acids such as oleic acid or branched chain carboxylic acids such as naphthenic acid with a molecular ff of 1200 to 500. preferable.

This is because the obtained copper carboxylate is easy to handle and has good solubility. Useful oil-soluble copper has the formula (RR
'NC85) nCu (where n is 1 or 2, R, R
' are the same or different hydrocarbon radicals containing 1 to 18, preferably 2 to 12 carbon atoms, such as alkyl, alkenyl, aryl, aralkyl, cakaryl,
and alicyclic group). Particularly preferred R, R' groups are alkyl groups having 2 to 8 carbon atoms. Thus, the radicals include, for example, ethyl, n-propyl, 1--10pyl, n-7'thyl, t-ethyl, sec-butyl, amyl, n-hexyl, l-hexyl
n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl 1-phenyl, methylphenyl, cyclohexyl, methylcyclo can be methyl, pro is nyl, butenyl, etc. To obtain oil solubility, the total number of carbon atoms in R and R' is generally about 5 or more. Copper sulfonates, phenates, and acetyl heptatonates can also be used.

Examples of useful copper compounds include copper (Cu' and/or Cu'') salts of alkenylsuccinic acids or anhydrides.

These salts may be basic, neutral or acidic.

These can be obtained by reacting (a) an optional component in the ashless dispersant portion described above having at least one carboxylic acid (or anhydride) radical with a reactive metal compound. Suitable acid (or anhydride)-reactive metal compounds include ferrous or cupric hydroxides, oxides, acetates, borates, carbonates or basic carbonates.

Examples of the metal salt of the present invention include Cu salt of polyisobutylene succinic anhydride (hereinafter referred to as Cu-PIBSA) and Cu salt of polyisobutylene succinic acid. Preferably, the metal salt used is selected to be divalent Cu+ 2. A preferred material has an alkenyl group with a number average molecular weight of about 70.
It is a polyalkenylsuccinic acid having 0 or more. The alkenyl group desirably has about 900 to 1400, more broadly 2
It has an average molecular weight of up to 500, most preferably about 950.

Among the dispersants listed above, particularly preferred is polyisobutylene succinic acid (PIBSA). These materials may be dissolved in a solvent such as mineral oil and then heated in the presence of an aqueous solution (or slurry) of the gold-hole-containing material. Heating is carried out at 70-200°C, preferably 110-140°C. Depending on the type of salt produced, it is necessary to prevent the reaction from being carried out at temperatures above 140° C. for a considerable period of time, for example 5 hours or more, thereby preventing decomposition of the salt.

Copper antioxidants (e.g. Cu-PIBSA,
Cu-oleate, mixtures thereof) are generally about 50
~500 ppm gold kjS (metal in lubricating oil composition or fuel composition) is used.

Copper antioxidants are inexpensive and effective at low concentrations;
Has little impact on product cost. The results obtained are superior to the conventional, expensive, antioxidants used in filtration. In the amounts used, copper does not affect the properties of the other components of the lubricating composition.

In incorporating an effective amount of copper antioxidant into the lubricant composition, the effective amount is about 5 to 50% based on the total amount of the lubricant composition.
0 ppm, preferably 10 to 200 ppm 1 More preferably 20 to 130 ppm (e.g. 90 to 120 ppm
ppm). Of course, the preferred amount will depend on other factors that affect the quality of the lubricant base oil.

Corrosion inhibitors prevent oxidation of non-ferrous metal parts.

14 Examples of anti-food agents include phosphorus-sulfurized hydrocarbons, which are further combined with alkaline earth metal compounds or hydroxides,
Preferred examples include alkylated phenol or alkylphenol thioester, and those reacted in the presence of carbon dioxide. Phosphorous sulfurized hydrocarbons are produced by mixing hydrocarbons such as heavy petroleum components such as C2-C6 olefin polymers such as terpenes and polyisobutylene with 5-50% weight of phosphorus for about 0.5-15 hours at 65°C. It can be produced by reacting at a temperature of ~320°C. Further, neutralization of phosphorus-sulfur hydrocarbons can be performed by the method described in US Pat. No. 1,969,524.

Other antioxidants may be used in addition to component B to reduce the tendency of mineral oils to degrade during use, thereby reducing the formation of oxides such as face deposits and sludge on metal surfaces. May be desirable.

Such antioxidants preferably include alkaline earth metal salts of alkylphenol thioesters having 05-C12 alkyl side chains (calcium nonylphenyl sulfide,
Barium t-octylphenyl sulfide, etc.), diphenylamine, alkyldiphenylamine, dioctyl phenylamine, phenyl alpha naphthylamine (and its alkylated derivatives), phosphorus-sulfurized hydrocarbons, other sulfurized hydrocarbons (sulfurized phenol, sulfurized alkylcatechol, etc.) ), phenols, hinkoutphenols,
Includes bisphenols, catechols, alkylated catechols, etc.

Friction modifiers can impart appropriate *m characteristics to lubricating oils such as automatic transmission fluids.

Such modifiers include the fatty acid esters and amines described in U.S. Pat. No. 5,955,659, U.S. Pat. No. 417
Polyisobutenylsuccinic anhydride described in No. 6074
Molybutene complexes of aminoalkanols, US Pat. No. 4j
Glycerol esters of dimeric fatty acids as described in US Pat. No. 05571, alkane phosphates as described in US Pat.
Reaction product of onate and oleamide, US Pat. No. 385
No. 2205, S-carboxy-alkylene hydrocarbyl succinimide, S-carboxy-alkylene hydrocarbyl succinic acid and mixtures thereof; Examples include di(lower alkyl) phosphites and epoxides described in Patent No. 5,932,290, phosphorus-sulfated N-(hydroxyalkyl)alkenyl succinimide and alkylene oxide adducts as described in U.S. Pat. No. 4,028,258, and the like. The most preferred friction modifiers are glycerol heptano and dioleates, succinates, or metal salts thereof, and thiobisalkanols (U.S. Pat. No. 43,448).
No. 53).

Pour point depressants lower the minimum temperature at which flow can occur. Examples of depressants or regulators that optimize low-temperature fluidity include C8~
There are C18 dialkyl fumarate and vinyl acetate copolymers, polymethacrylates, and wax naphthalenes.

Antifoaming agents can be polysilicone, such as silicone oil and polydimethylsiloxane.

Organic oil-soluble compounds that can be used as rust preventives include nonionic surfactants such as polyoxyalkylene polyols and their esters, and anionic surfactants such as alkyl sulfonates. The nonionic surfactant that can be used as a rust inhibitor in the oil-based composition of the present invention usually exhibits surface-active properties due to a large number of weakly stable groups such as ether linkages. Such an activator reacts an organic substance having active hydrogen with an excess amount of lower alkylene oxide (ethylene oxide, propylene oxide, etc.) to alkoxylate it until a predetermined alkoxy group is introduced into the molecule.

Preferred rust inhibitors are polyoxyalkylene polyols and their derivatives. This type of material is commercially available from various companies, including one available under the trade name Pluronic Polyo 1g from Wine Todd Chemicals Corporation (USA), ethylene oxide and polypropylene oxide available from The Dow Chemical Company;
Dodecylphenyl or monophenyl polyethylene glycol esters and U
These include polyalkylene glycol and its derivatives under the name eonO. These are just a few examples of commercial products suitable for addition as rust inhibitors to the improved lubricating oil compositions of this invention.

In addition to polyols, esters obtained by reacting these polyols with various carboxylic acids are also suitable.

Suitable acids for preparing these esters include lauric acid, stearic acid, succinic acid, alkyl-substituted or alkenyl-substituted succinic acid (substituents containing up to about 60 carbon atoms).

Preferred polyols are block polymers @ therefore:
Hydroxyl group-substituted compound R-(OH) n (n = 1 to 6
, R is a residue of a mono- or polyhydric alcohol such as phenol, naphthol, etc.) is reacted with propylene oxide to form a lipophilic base.

By reacting this base with ethylene oxide, a parent group is introduced, resulting in a molecule having lipophilic and hydrophilic parts. The relative dimensions of these parts depend on the quantity ratio of the reactants,
It can be adjusted by changing factors such as reaction time. It is easy to produce polyols whose molecules have lipophilic and hydrophilic parts, and the proportions of these parts are suitable for a given lubricating oil composition, regardless of differences in base oil and other additives. It can be done.

If greater oil solubility is desired in a particular lubricating oil composition, the lipophilic portion may be increased or the hydrophilic portion may be decreased. If greater oil-in-water emulsion separation capacity is required, the hydrophilic and/or lipophilic moieties can be adjusted.

R-(OH) includes alkylene glycols such as alkylene glycol, alkylene triol, and alkylene tetrol (ethylene glycol, furopylene gellicol, chrycerol, pentaerythritol, sorbitol, mannitol, etc.).

Other suitable polyols are commercially available from Weintodt Chemicals Company under the name Pluronic Polyyol and are particularly suitable as corrosion inhibitors.

The polyol is a compound corresponding to the following formula.

OH3 However, X17 and 2 are integers of 1 or more, -CH2CH2
The 0-group is selected such that it accounts for about 10 to about 40% of the total glycol molecular weight, and the average molecular weight of the glycol is about 1
000 to about 5000. These materials are produced by first condensing propylene oxide with propylene glyfur to form an OH field and then reacting with ethylene oxide to form hydrophilic moieties at both ends of the molecule. For best results, the ethylene oxide units should be about 10 to about 40% of the molecule. Molecular weight is approximately 2500
~50oO, and the ethylene oxide moiety is approximately 10% of the molecule.
Polyols containing ~15% are particularly suitable. Molecule 11 is about 400 and about 10% is CH2CH2O
Particularly good are such polyols which are dominated by units.

Alkoxylated aliphatic amines, amides, alcohols, and C9-C16 alkyl-substituted phenols (e.g. hamono,
Alkoxylated fatty acid derivatives treated with (di-heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecylphenols) can also be used. These are described in US Pat. No. 5,849,501.

In addition to the above additives, metal-containing additives such as barium and sodium may also be used in the lubricant composition of the present invention.

Other suitable additives are polythiosulfamide thiazicozoles, which are described in British Patent No. 1,560,850. When using these, CLO1 of the lubricant composition
~Type 10 O1 ~ Preferably used in an amount of 0.1 to 5.0% by weight.

Some of these additives have more than 20 functions simultaneously. These additives, such as dispersants and antioxidants, perform their normal functions when mixed with the base oil in effective amounts. Examples of useful proportions for complete lubricating oil compositions are shown below.

Preferred Range Weight % Wide Range Weight % Component A
4-7 5-10 Component B 2.
2-4 2-6 component CQ, 2-α4 α1
~α6 Viscosity modifier 0-4 0-12 Corrosion inhibitor α01-CL5 0-t5 Antioxidant 0-tS O-5 Pour point modifier 0.01-CL5. 01~t O antifoaming agent Q, 001~α01. 001~Q,
1 Non-metallic anti-wear agent α001~tS O~5 Friction modifier 0.01~tS O~5 Lubricating oil base oil Remaining part When using other additives, the novel detergent-anti-wear agent of the present invention It is desirable (but not necessary) to provide a concentrated solution or dispersion of the mixture with one or more of the other additives mentioned above.

This allows several types of additives to be added to the base oil at the same time? ! !
A lubricating oil composition can be formulated. Dissolution of the additive concentrate into the lubricant base oil is facilitated (but not required) by using a solvent followed by heating. This concentrate contains appropriate amounts of additives to provide a predetermined concentration when mixed with the base oil in a predetermined proportion. Accordingly, the detergent-antiwear mixture of the present invention can be mixed with other desired additives in a small amount of base oil or compatible solvent to
A concentrate (additive package) is formulated containing the active ingredients at a concentration of about 90% (sum of all ingredients). Preferred concentrations are about 15 to 75%, most preferably about 25 to about 60% (by weight). .

The final lubricant composition typically consists of about 10% concentrate and the balance base oil.

Note that in this document, % weight refers to the active ingredient (AI) and is based on the total weight of the concentrate and the total weight of the lubricating oil composition (additive base oil + thinner).

Completely formulated 5AE15W with component proportions shown in Table I
40 lubricating oil compositions were produced. However, each component in the table (1)
or 9) is as follows.

(1) 5.93 Mao 1% polyisobutylene succinamide (t58 weight%N, 950Mn PIB (polyisobutylene), S A (succinamide)/BIB molar ratio 10Sα65%B, 515% AI and , t6
4% polyisobutylene succinamide (t46
mht%N, 1300MnP I B55A/PIB%
Mixture with t2.0.52 mm% B150.8 wt.% AI).

The SA/PIB molar ratio is the number of moles of succinic anhydride per mole of polyisobutylene used to react to form the described succinic anhydride. is the molar ratio.

(2) Sulfurized nonylphenol (70 wt% AI), 7 wt% 51 (6) Comparative Example A-145 Mao 1% zinc dihydrocarbyl dithiophosphate (ZDDP), an anti-wear agent with 8 alkyl groups (this one P2O5 is reacted with isooctyl alcohol to give about 7% phosphorus by weight),
α30 vo1% ZDDP whose alkyl group is a mixture of about 4 to 5 carbon atoms (this is P2O5
Comparative Example B and Example 1.2 Comparative Example B and Example 1.2
-145vo1% ZDDP with alkyl group having 8 carbon atoms
(This product is made by reacting P2O5 with isooctyl alcohol to make it about 7% phosphorus).

(4) Overbased magnesium sulfonate (based on alkylbenzenesulfonic acid), 400TBN15t7 heavy fit%
(AI), 92% Mg detergent by weight.

(5) 2,5-bis(nonyldithio)13,4-thiadiazole anticorrosion agent (Amoeo 15 B, manufactured by Amofu Chemical Company).

(6) Comparative Example A and Example 1 - Ethylene Propylene Copolymer Viscosity Index Improver Concentrate (43 wt% ethylene,
2.8 thickening efficiency, 10fi1% AI).

(7) Mainly 5olvsnt 150 natural base oil.

(8) Total number of bases - measured according to ASTM D2896.

(9) Total sulfated ash 51 - Measured according to ASTM D874.

Table ■ Examples Examples Examples Examples, AB12 PIBSA-PAMfil agent (1) 157 5.
54 757 7:57 Viscosity index modifier (6)
8.82 -- 8.20 8.50 base oil
(7) Remainder Remainder Remainder
Remaining TBN (8mm a4
ao 5.0 2.4SAS
I ((9) Q, 85 (L84
(L440 The above lubricating oil composition was added to Cummins NTC-
In the 400-driving test (load = total weight of refrigerated trailer 18,000 bonds), the vehicle was destroyed under approximately 80% load condition. It was mostly used for shipping between Dallas in the United States and the Pacific Northwest. The diesel fuel used contained (less than 15% by weight sulfur).

The following 5AE15W40? for the above test? Tests for A lubricant were also included. These compositions contained an ashless dispersant, an overbased alkaline earth metal detergent and inhibitor, and a zinc dihydrocarbyl dithiophosphate antiwear agent.

Table ■ Cto 10 D tl 12 E α72 & 9 F to 10 G to 8 Hlo 8 I tO8 J α97 K t95 14 As a result of the above, the table results were obtained.

ABCDg Fuel 9 (miles/gal) 196K 207K 175
K 195K 211 average sludge 9.8
4 9.7B 9.76 9.85 9.75
TGF% 67 40 40
70 56 2nd GF% 59 59
54 40 85th 30th F% 8
5 0 1 154G Disadvantage Q, 59 t29 α52 Q,
67 T86 polished carbon% 17 55
59 35 29 Clean% 1
0001 All Land Demerits 2t59 2442
28.8 22.75 5437 Crown Lower 15
．． 15 5.44 t88 551 1α0
0TTL not counted ii1# 957 115 1
19 138 199 total) 1 #
987 1075 872 889 2144YukeiiMI/QT 524 475 609
1024 450 cylinder inner surface maximum mA (in), ools, ools
,0028. 0018, a, o2s average maximum
z (In), 0012. 0012. 0022
．． 0012. 0021 Wear rate 1n/10100QK
,0006. 0006.0015. 0006.
0010 Holding horn 86 95 95
95 92 Koken, -77228 2,03+, 050. 028. 060. 02
85. 024. 027. 025
．． 029. 026 Note Piston evaluation unknown, local personnel used cleaning manual.

Table ■ 189 ni Mine 187K 175K 200K 183K
177K 190K 12.8168 to 9.819.7
69.759749.739.7B 9.78 Q, 0
49.76-73 404776 505019.86
6-6 5 6 105 5.94.42-α65α7
1α21121α7α92α66t8157 2245
15622α217. d 104539554952
3537.11t0510 5 8 0 0 5 16
2.612-5t472B, 1127. ．． 5555.
142 (1427,865,428,4-5194.1
9 engineering 694.882-0 4゜592.517.8-1
801401? ! 7185137151729. O15
8-15741022106918407051217
4711! r5551561269451255261
35562C15559,0025,000B,00
22.0017.0015.0015.00185.0
006.0017.0025.0007.0015.0
015, Q, 015.0015.0015.0005
J1017.0012. 0004. 000?
,0007. 0007. 0007
, mouth 008. 0005. 001092 B89
492958090.64.980797979&72
．． 59 ooooooo.

The expression shows that the Example 1.201 lubricating oil composition keeps the piston crown land clean without sacrificing any remaining performance.

The ashless lubricating oil compositions of the present invention are useful in heavy duty tape easel engines using roller cam 7 lowerers. The ashless lubricating oil composition of the present invention is preferably 1% by weight or less, more preferably 0.5% by weight or less, even more preferably 3% by weight or less (for example, 0.1 to 0.3% by weight).
, most preferably 1% (e.g. 100-500
It can be particularly suitably used in heavy-duty diesel engines using fuel oil containing sulfur (ppm). Such oily fuels include hydrocarbon petroleum distillate fuels such as diesel fuel and fuel oil as defined by ASTM D396. Compression ignition engines use non-hydrocarbon substances such as alcohols, ethers, and organonitro compounds (
Normally liquid fuels such as methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane, etc.) can also be used. Vegetable oils and mineral oils (eg, corn oil, alfalfa, shale, and coal oil) are also possible fuels. It is also possible to use mixtures of one or more hydrocarbon fuels and one or more non-hydrocarbon fuels. For example, a mixture of diesel fuel and ether. A particularly preferred fuel is diesel fuel.

The lubricating oil composition of the present invention is applied to a cylinder (usually engine 1).
(1 to 8 or more per unit) are used by charging them into the crankcase. The cylinder houses a piston that reciprocates in a vertical cycle, and the piston has an airtight land (top).
has. That is, there is a minimum distance between the piston top and the cylinder inner wall liner in order to minimize the amount of particulate matter generated within the cylinder combustion chamber. Such a sealed top provides improved fuel economy and increases cylinder compression efficiency. The top generally also includes the portion of the cylindrical surface above the piston ring groove. The top therefore has a circular cross section when cut at right angles to the length aha of the piston. The outer part II4 of the top part is bored parallel to the vertical wall of the inner surface of the cylinder (cylindrical top part). Alternatively, the top may taper centrally from the groove of the piston ring toward the top surface of the piston, or a portion called the "crown." The gap between the top and the inner wall of the cylinder is called the "top gap." For the “cylindrical top”, this top gap is approximately CL25111$~α751IjI
It is. Approximately 116-0.76u at the tapered top.

More preferably α25 to 0.51M, the top gap at the top surface (value of the position of the crown of the piston) is about CL25 to t14m111, preferably about Q, 3
It is 8-0.76m. The top gap may be smaller than the above values provided that undesired top-to-cylinder liner contact (leading to liner failure) does not occur during engine operation. Generally, the height of the top (vertical distance from its base to the top surface) is approximately 2.54
~6α5 trend, usually about 20.3 to 3Q, 5m (for 4-stroke diesel engine) or about 2.54 to 12.
71111 (for 2-stroke diesel engine).

Claims (25)

[Claims] (1) Oil with lubricating viscosity accounts for the majority of the ingredients, and minor ingredients include (A) 3% by weight or more of at least one ashless dispersant, and (B) 2% by weight or more of at least one sulfurized alkylphenol. and (C) 0.1% by weight or more of at least one organic sulfur compound of the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R^4 and R^5 have 2-30 carbon atoms) a straight-chain or branched alkyl group, a cyclic group, or an alicyclic group, an aryl group, an alkylaryl group, or an arylalkyl group, where w and z are 1-8), and the total sulfated ash content ( A heavy duty diesel lubricating oil composition, wherein the amount of SASH) is less than 0.01% by weight. (2) Ashless dispersants include oil-soluble salts, amides, imides, oxazolines, and esters, mixtures thereof, long-chain hydrocarbon group-substituted mono- or dicarboxylic acids, or their anhydrides (where the long-chain hydrocarbon group is C_2 ~C_1_0 monoolefin and its number average molecular weight is 700-5000)
The lubricating oil composition according to item 1 above, which is at least one selected from the group consisting of: (3) Long-chain hydrocarbon group-substituted mono- or dicarboxylic acid contains polyolefin at 0.00% per mole thereof. 2-20 moles of alpha or beta unsaturated C_4-C_
The lubricating oil composition according to item 2 above, wherein the lubricating oil composition is substituted with a 1_0 monounsaturated dicarboxylic acid-forming substance. (4) The lubricating oil composition according to item 3, wherein the alpha- or beta-unsaturated C_4 to C_1_0 monounsaturated dicarboxylic acid-producing substance is a dicarboxylic acid, or an anhydride or ester thereof. (5) The lubricant according to item 3 above, wherein the dicarboxylic acid or anhydride or ester thereof is fumaric acid, itaconic acid, maleic chain, maleic anhydride, chloromaleic acid, dimethyl fumarate, and chloromaleic anhydride. oil composition. (6) The long-chain hydrocarbon group-substituted mono- or dicarboxylic acid is a polyolefin substituted with a group selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. oil composition. (7) The ashless dispersant is polyisobutylene succinimide of a polyalkylene polyamine having an average of 2 to 60 carbon atoms and 1 to 12 nitrogen atoms per mole of the polyamine below, and the polyisobutylene portion is on average The lubricating oil composition according to item 1 above, which is polysobutylene having a molecular weight of 800-3000. (8) The lubricating oil composition according to item 2 above, wherein the SASH is zero. (9) The ashless dispersant is (a) an olefin polymer having a number average molecular weight of 700-5000, C_2 to C_
A long-chain hydrocarbon group-substituted C_4 to C_1_0 monounsaturated dicarboxylic acid-forming substance obtained by reaction with a 1_0 monounsaturated dicarboxylic acid, which is present in the mixture used to form the carboxylic acid-forming substance. and (b) a nucleophilic reactant selected from the group consisting of amines, alcohols, amino alcohols, and mixtures thereof. The lubricating oil composition according to item 1. (10) The lubricating oil composition according to item 9, wherein the nucleophilic reactant is an amine. (11) The lubricating oil composition according to item 10, wherein the amine has 2 to 60 carbon atoms and 1 to 12 nitrogen atoms per molecule. (12) The lubricating oil composition according to item 11 above, wherein the amine has 2 to 40 carbon atoms and 1 to 9 nitrogen atoms per molecule. (13) The lubricating oil composition according to item 12, wherein the amine is polyethylene polyamine and the reactant is borated. (14) The amine has 3 to 9 nitrogen atoms per molecule, and the hydrocarbon group-substituted carboxylic acid-forming substance has 0.1 to 1.0 moles of succinic acid contained in the olefin. 11. The lubricating oil composition of claim 10, containing an amount of succinic acid that is reacted with an equivalent amount of succinic acid. (15) The reaction product is 0. 05-14 containing 2.0% by weight of boron
The lubricating oil composition described in . (16) The lubricating oil composition according to item 15, wherein 2 moles or more of the carboxylic acid-forming substance is contained per mole of the nucleophilic reactant. (17) The lubricating oil composition according to item 17, wherein the ashless dispersant is borated and the reaction product mixture contains boric acid. (18) The lubricating oil composition according to item 17, wherein the olefin polymer is polyisobutylene. (19) The number average molecular weight of the olefin polymer is 1500-3000, and the amine is
- The lubricating oil composition according to item 18, having 7 nitrogen atoms. (20) (A) 10-70% by weight of at least one oil-soluble ashless dispersant; (B) 10-40% by weight of at least one sulfurized alkylphenol; and (C) 0.5% by weight of at least one sulfurized alkylphenol.
-5% by weight of at least one organic sulfur compound of the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R^4 and R^5 are linear or branched alkyl groups having 2-30 carbon atoms; , a cyclic group, or an alicyclic group, an aryl group, an alkylaryl group, or an arylalkyl group, and w and z are 1-8); and 30-80% by weight of a base oil. Concentrated additive for use. (21) To improve the performance of engine lubricating oil compositions for heavy-duty diesel engines powered by normally liquid fuels with a sulfur content of less than 1% by weight, the total sulfated ash (SASH) of the oil is The metal content is adjusted to 0.01% by weight or less, and the oil contains (A) at least 3% by weight of at least one ashless dispersant, and (B) at least 2% by weight of at least one kind of ashless dispersant. A sulfurized alkylphenol and (C) at least one organic sulfur compound of the following formula with a copper corrosion inhibition amount ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R^4 and R^5 have 2-30 carbon atoms a straight-chain or branched alkyl group, a cyclic group, an alicyclic group, an aryl group, an alkylaryl group, or an arylalkyl group, and w and z are 1-8). A method for producing a lubricating oil composition. (22) To improve the performance of diesel lubricating oils for use in heavy-duty diesel engines with at least one gas-tight top surface piston, the total sulfated ash (SASH) content of said oil is less than or equal to 0.01% by weight. The metal content is adjusted so that the fuel oil contains (A) at least 3% by weight of at least one ashless dispersant, (B) at least 2% by weight of at least one sulfurized alkylphenol, and (C) Copper corrosion inhibiting amount of at least one organic sulfur compound of the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R^4 and R^5 are straight or branched chain alkyl groups having 2-30 carbon atoms , a cyclic group, or an alicyclic group, an aryl group, an alkylaryl group, or an arylalkyl group, and w and z are 1-8). Method. (23) The concentrated additive of claim 22, used in conjunction with a normally liquid fuel having a sulfur content of less than 1% by weight. (24) a lubricating oil crankcase of a diesel engine comprising a crankcase and at least one airtight top surface piston, a majority of the oil having a lubricating viscosity;
) 3% by weight or more of at least one ashless dispersant;
B) 2% by weight or more of at least one sulfurized alkylphenol, and (C) at least one organic sulfur compound of the following formula with an amount of copper corrosion inhibition 5 is a straight-chain or branched alkyl group, cyclic group, or alicyclic group, aryl group, alkylaryl group, or arylalkyl group having 2-30 carbon atoms, and w and z are 1-8) A lubrication method comprising charging a lubricating oil composition in which the metal content is adjusted so that the total sulfated ash (SASH) content is 0.01% by weight or less. (25) The method of claim 24, wherein the diesel engine is used with a normally liquid fuel having a sulfur content of less than 1% by weight.