JP2012193386A - Lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To create a lubricating agent satisfying strict requirement of the ring conglutination test, and simultaneously satisfying other standards.SOLUTION: SAE OW-30 or 5W-30 or 5W-20 lubricant agent has <15 Noack volatility, optionally ≤1.5% M-111 fuel economy; and <100 ppm chlorine content. The lubricant agent includes: a base stock comprising 0 to <10% group I and/or group II base stock; a molybdenum additive providing ≤1,000 ppm molybdenum to the lubricant agent; a calcium cleaning agent providing a surfactant of ≥10 mM per 1 kg molybdenum; one or more other additives; and a viscosity modifier.

Description

  The present invention relates to multi-grade lubricating oil compositions, particularly compositions with improved performance in diesel engine ring fit tests.

Lubricating oil compositions (or lubricants) for crankcases of internal combustion engines are well known, and it is also well known that the compositions contain additives (or additive components) to improve their properties and performance.
Increasingly, the requirements to meet the performance standards of companies that sell other companies' products under their own brand (OEM) are related to the properties of the lubricant. One such performance criterion is related to piston ring sticking during operation of a compression ignition (diesel) internal combustion engine. This is usually referred to simply as “ring attachment” and can be measured by the VWTDi test (CEC L-78-T-97).

Other important performance criteria include lubricant volatility, lubricant fuel economy performance, and lubricant chlorine content.
The various criteria clearly constrain the lubricant formulation with respect to the additive components and amounts that can be used and the base stock.
Surprisingly, according to the present invention, the low concentration of molybdenum present as an organomolybdenum compound can be used to produce a lubricant that meets stringent “ring-fitting” test requirements while simultaneously meeting other criteria. Was found.
A number of documents describe the use of oil-soluble molybdenum in lubricants. For example, U.S. Pat. Nos. 4,164,473, 4,176,073, 4,176,074, 4,192,757, 4,248,720 No. 4,201,683, 4,289,635 and 4,479,883. However, none of these describes the use to improve “ring adhesion”.

U.S. Pat. No. 4,164,473 US Pat. No. 4,176,073 US Pat. No. 4,176,074 US Pat. No. 4,192,757 U.S. Pat. No. 4,248,720 U.S. Pat. No. 4,201,683 U.S. Pat. No. 4,289,635 U.S. Pat. No. 4,479,883

In a first aspect, the present invention provides a Noack volatility according to CEC L-40-A-93 of less than 15% mass loss, such as less than 13% mass loss, preferably less than 11% mass loss, preferably 4 or 5%. It is a SAE 0W-30 or 5W-30 or 5W-20 multigrade lubricating oil composition that has a mass loss or greater and that the M-111 fuel economy according to CEC L-54-T-96 may be 1.5% or more. And the following composition (A) to (E) or produced by mixing the following (A) to (E):
(A) 0 to 10% by weight of a Group I base stock or a Group II base stock or a mixture of a Group I and Group II base stock other than the base stock generated from the supply of additive components in the composition Less than, preferably less than 0 to 5% by weight of a base stock of a large amount of lubricating viscosity; and a small amount of additive components containing the following (B) to (E):
(B) In the composition, one or more molybdenum-containing additions in an amount providing elemental molybdenum of 1000 ppm by weight or less, preferably 500 ppm by weight or less, such as 350 or 300 or 250 ppm by weight, for example 50 ppm by weight or more. Agent;
(C) Addition of one or more calcium detergents containing as a surfactant a calcium salt of an organic acid in an amount providing 10 mmol or more, for example 12 mmol or more, for example 30 or 35 mmol, of surfactant per kg of composition Agent;
(D) One or more other lubricating oil additives selected from ashless dispersants, metal detergents, antioxidants, antiwear agents, and friction modifiers (provided that these additives are the above-mentioned (B) And (E) different from (C)); and (E) one or more viscosity modifiers, wherein these additive components are less than 100 ppm by weight, for example less than 50 ppm by weight, but more than 5 or 10 ppm Chlorine is provided to the composition.)
I will provide a.

In a second aspect, the present invention provides a method of lubricating a compression ignition internal combustion engine comprising operating a compression ignition internal combustion engine and lubricating the engine with the lubricating oil composition of the first aspect of the present invention. To do.
In a third aspect, the present invention provides a method for reducing the ring sticking tendency of a compression ignition internal combustion engine comprising adding the lubricating oil composition of the first aspect of the present invention to a compression ignition internal combustion engine. .
In a fourth aspect, the present invention provides a combination comprising a crankcase of a compression ignition internal combustion engine for lubricating the crankcase and the lubricating oil composition of the first aspect of the present invention.

In this specification,
“Contains” or like terms specify the presence of a described feature, integer, process or component, but the presence or addition of one or more other features, integers, processes, components or collections thereof. Not to exclude;
“Major amount” means an amount greater than 50% by weight of the composition;
“Small amount” means less than 50% by weight of the composition and is calculated as the active ingredient of the additive, both for the specified additive and for the total weight percent of all additives present in the composition;

As used herein, “oil soluble” or “dispersible” does not necessarily mean that the compound or additive can be soluble, soluble, miscible or suspended in the oil in all proportions. However, these terms mean, for example, that the oil is soluble or can be stably dispersed to such an extent that the desired effect can be sufficiently exerted in the environment in which the oil is used. Furthermore, the specific additive can be introduced at a higher concentration if desired by further introducing another additive.
The present invention also provides products obtained or products obtained as a result of reaction between various additive components of the composition or concentrate, which are essential, conventional and optimal under the conditions of formulation, storage or use. .
The features of the invention are described in more detail below.

Multigrade lubricants Multigrade lubricants operate over a wide temperature range. Typically, it is represented by a description such as SAE 10W-30 or SAE-5W-30. The first number in the multigrade descriptor is related to the safe crank temperature (eg −20 ° C.) viscosity requirement of the multigrade oil as measured by the cold crank simulator (CSS) under high shear rate (ASTM D 5293) . In general, the lower the CSS viscosity of the lubricant, the easier it is to crank the engine at lower temperatures and the ability to start the engine at ambient temperature is improved.

Multi-viscosity grade oils, commonly referred to as “multi-grade”, are designed to operate over a wide temperature range and are represented by descriptors such as SAE 10W-30 or SAE 5W-30. Their characteristics are specified in the document SAE J300 of the Automotive Engineering Association. This publication has two criteria:
-Multigrade is defined by the coldest crank and pump viscosities,-the highest and lowest kinematic viscosity at 100 ° C and the lowest high shear viscosity at 150 ° C and 10 ⁸ s ^-1 .
The low temperature characteristic defines which “W” grade is assigned to the lubricant, and the high temperature characteristic defines the “not W” part of the name.

SAE J300 prescribes the W grade series by expressing the operating requirements at the lowest temperature at SAW 0W. SAE 5W, 10W, 15W, 20W and 25W also specify that these grades are suitable for increasingly higher minimum operating temperatures.
Non-W grades are displayed numerically, which define an increasing high temperature viscosity scale. The scale starts with SAE 20 and reaches SAE 30, 40 and 50, the most viscous grade SAE60.
This automotive crankcase lubricant viscosity classification system is universally applied to the vehicle and lubricant manufacturing industries.

Noack volatile oil volatility is related to both undesirable oil consumption and emissions in the technical literature. One of the methods used to measure lubricant volatility is the Noack method. Two standardized Noack methods are the JPI method 5S-41-93 and CEC L-40-A-93. By these methods, the mass loss% after the sample is kept at 250 ° C. for 60 minutes in a state where air passes is measured. For the purposes of the present invention, all Noack volatility measurements were performed using an apparatus calibrated with a control fluid.
Fuel economy
The M-111 fuel economy was measured by CEC-L-54-T-96.

(A) Base stock Base stock (sometimes referred to as “base oil”) is an oil having a lubricating viscosity and is the main liquid of the lubricant for blending additives and other oils to produce the final lubricant. It is an ingredient.
Base stocks can be classified into groups I-V according to the API Engine Oil Authorization and Warranty System (EOLCS) API 1509 definition used to define the base stock of the present invention. Therefore;
a) Group I base stocks containing less than 90% saturates and / or more than 0.03% sulfur and having a viscosity index of 80 or more and less than 120 using the test method specified in Table E-1 is there.

b) Group II base stock contains 90% or more of saturates and 0.03% or less of sulfur and has a viscosity index of 80 or more and less than 120 using the test method specified in Table E-1.
c) Group III base stock contains 90% or more of saturates and 0.03% or less of sulfur and has a viscosity index of 120 or more using the test method specified in Table E-1.
d) Group IV base stock is polyalphaolefin (PAO).
e) Group V base stock includes all other base stocks not included in Group I, II, III or IV.

(B) Molybdenum-containing additive Molybdenum can be used, for example, with oxidation values IV and V, as is known in the art. Molybdenum can exist as a cation, but this is not absolute. Thus, for example, molybdenum-containing composites can be used.
Examples of molybdenum compounds that can be used include molybdenum salts of inorganic and organic acids (see, for example, US Pat. No. 4,705,641), in particular monocarboxylic acids having 1 to 50 carbon atoms, preferably 8 to 18 carbon atoms. Molybdenum salts, such as molybdenum octanoate (preferably 2-ethylhexanoate), naphthenate or stearate; molybdenum trioxide, molybdic acid or alkali metal salts thereof (or such molybdenum compounds and reducing agents) Reaction product) and a reaction product of a secondary amine having a hydrocarbon group having 6 to 24 carbon atoms (see European Patent Publication No. 205165); disclosed in European Patent Publication No. 404650 Less preferred due to overbased molybdenum-containing complex, molybdenum dithiocarbamate and phosphorus content, but molybdenum dithio And oil-soluble molybdenum compounds disclosed in US Pat. Nos. 4,995,996 and 4,966,719, preferably molybdenum xanthates and trixanthates described in these specifications; Sulfur-containing composites are included. Specific examples of molybdenum- and sulfur-containing composites include those produced by reacting an acidic molybdenum compound with a basic nitrogen-containing material and reacting with a sulfur source (e.g., British Patent No. 2097422). And a triglyceride and a basic nitrogen compound to form a reaction product, and the reaction product and an acidic molybdenum compound to react to form an intermediate reaction product. And a product produced by reacting a body product with a sulfur-containing compound (for example, see British Patent No. 2220954). Other examples of molybdenum compounds are described in International Patent Application No. PCT / IB97 / 01656, which contains a trinuclear molybdenum core and contains non-metallic atoms consisting entirely or partly of sulfur. Well, the core is bound to a ligand that can make the compound oil-soluble or oil-dispersible. The compound has the general formula Mo ₃ S _k L _p , wherein L represents a ligand, such as dithiocarbamate, P is in the range of 1-4, and K is at least 4, preferably 4-10, preferably 4-7).

( C) Calcium detergent detergent is an additive that reduces the formation of piston precipitates, such as hot varnish and lacquer precipitates, in engines; generally, it has acid neutralizing properties and is a finely divided solid Can be suspended. Most detergents are based on metal “soap”, which are metal surfactants or salts of acidic organic compounds.
The detergent generally contains a polar head with a long hydrophobic tail, which contains a metal salt of an acidic organic compound. The salt can contain a substantially stoichiometric amount of metal and is usually described as a normal or neutral salt, typically having a total base number of 0-80, ie TBN (measured by ASTM D2896 Can have). A large amount of the metal base can be contained by reacting an excess metal compound such as an oxide or hydroxide with an acidic gas such as carbon dioxide. The resulting overbased detergent contains neutralized detergent as the outer layer of a metal base (eg, carbonate) micelle. Such overbased detergents can have a TBN of 150 or more, typically 250 to 450 or more.

Calcium detergents that can be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates. Particularly convenient calcium detergents are neutral and overbased calcium sulfonates having a TBN of 20 to 450, and neutral and overbased calcium phenates and sulfurized phenates having a TBN of 50 to 450.
Sulfonates can be prepared from sulfonic acids obtained by sulfonation of alkyl-substituted aromatic hydrocarbons such as those generally obtained from petroleum fractionation or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation can be carried out in the presence of a catalyst using an alkylating agent having 3 to 70 carbon atoms. The alkaryl sulfonate usually has 9 to 80, preferably 16 to 60, carbon atoms per alkyl-substituted aromatic moiety.

Oil soluble sulfonates or alkaryl sulfonic acids can be neutralized with calcium oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and esters. The amount of calcium compound is chosen so that the final product has the desired TBN, but generally ranges from about 100 to 220% by weight, preferably at least 125% by weight.
Calcium salts of phenol and sulfurized phenol are produced by reaction of phenol with a suitable calcium compound, such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods known in the art. . Sulfurized phenol is a compound in which phenol is reacted with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, and generally two or more phenols are bridged by a sulfur-containing bridge. It can be produced by obtaining a product that is a mixture.

( D) Other lubricant additives
Ashless dispersants are non-metallic organic materials that do not substantially form ash upon combustion. Its main function is to keep solid and liquid contaminants in suspension, which contains a long chain hydrocarbon to impart oil solubility and has a polar head that can associate with dispersed particles. Of note is a hydrocarbon-substituted succinimide.
Antioxidants increase the resistance of the composition to oxidation and work together with the peroxide and by modifying the peroxide to make them harmless by decomposing the peroxide or rendering the oxidation catalyst inactive. can do. Antioxidants include radical scavengers (eg, sterically hindered phenols, secondary aromatic amines, and organic copper salts); hydroperoxide degradation products (eg, organic sulfur and organophosphorus additives); Can be classified as multifunctionals. In practicing the present invention, certain benefits can be provided by the use or non-use of certain antioxidants. For example, in one embodiment, it is preferred that the lubricating oil composition of the present invention does not contain any secondary aromatic amine antioxidant. In another embodiment, one or more secondary aromatic amine antioxidants (e.g., in the range of 0.1 to 0.7%, preferably 0.2 to 0.5% by weight of the composition) and one or more of Combinations with sterically hindered phenolic antioxidants (e.g. in the range of 0.1 to 2%, preferably 0.5 to 1.5% by weight of the composition) in the lubricating oil composition of the present invention. Is preferably used. Such compositions can contain, for example, one or more molybdenum-containing additives in an amount to provide 50 or 100 ppm to 500 or 700 ppm by weight of elemental molybdenum in the composition.

Antiwear agents reduce friction and excessive wear and are usually based on compounds containing sulfur or phosphorus or both. Of note are metal dihydrocarbyl dithiophosphates such as zinc dialkyldithiophosphate (ZDDP). Preferably, the alkyl group is essentially a secondary alkyl group.
Friction modifiers include boundary additives that reduce the coefficient of friction and improve fuel economy. Specific examples include esters of polyhydric alcohols such as glycerol monoesters of higher fatty acids such as glycerol monooleate; esters of long chain polycarboxylic acids and diols such as butanediol esters of dimerized unsaturated fatty acids; Oxazoline compounds; and alkoxylated alkyl-substituted monoamines and alkyl ether amines such as ethoxylated tallow amines and ethoxylated tallow ether amines. In practicing the present invention, component (D) preferably contains one or more friction modifiers selected from esters of polyhydric alcohols and alkoxylated amines.

(E) Viscosity modifier A viscosity modifier (or viscosity index improver) imparts high temperature and low temperature operability to the lubricating oil. Viscosity modifiers that also act as dispersants are also known and can be produced as described above for ashless dispersants. In general, these so-called dispersant viscosity modifiers are used to derivatize functional polymers (eg, ethylene-propylene interpolymers post-grafted with an active monomer such as maleic anhydride), for example, with alcohols or amines. It is a thing.
Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters. Oil-soluble viscosity modifying polymers generally have a weight average molecular weight of 10,000 to 1,000,000, preferably 20,000 to 500,000. The average molecular weight can be measured by gel permeation chromatography or light scattering.

Representative examples of suitable viscosity modifiers include polyisobutylene, copolymers of ethylene, propylene and higher alpha olefins, polymethacrylates, polyalkyl methacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, styrene and acrylate esters. And interpolymers of styrene, partially hydrogenated copolymers of styrene, isoprene, styrene / butadiene, and isoprene / butadiene, and partially hydrogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene.
Other known additives different from those specified in the present invention may be included in the lubricating oil composition of the present invention. Examples of such additives include other detergents; rust inhibitors; corrosion inhibitors; pour point depressants; foam inhibitors; and surfactants. These can be used together in a ratio known in the art.
As is known in the art, certain additives can provide a variety of effects. Thus, for example, a single additive can function as both a dispersant and an antioxidant.
As mentioned above, the additive provides less than 50 ppm by weight of chlorine to the composition. Therefore, to meet this requirement, the use of chlorine-containing additives (such as those generated from manufacturing processes) should be eliminated or at least controlled.

In preparing a concentrate-defined lubricating oil composition, the additive is added to a suitable oily substance, typically a hydrocarbon, a carrier fluid, such as lubricating mineral oil, or other suitable solvent, in the form of an additive concentrate. It is usual to introduce. Oils of lubricating viscosity as described herein and aliphatic, naphthenic, and aromatic hydrocarbons are examples of suitable carrier fluids for the concentrate.
The concentrate constitutes a convenient means for handling the additive prior to use and for facilitating dissolution or dispersion of the additive in the lubricating oil composition. When preparing a lubricating oil composition containing one or more types of additives, each additive can be added separately—each in the form of a concentrate. However, in many cases it is convenient to provide a so-called additive “package” (sometimes referred to as an “adpack”) containing two or more additives in a single concentrate.
The concentrate can contain 1 to 90% by weight, for example 2 to 80% by weight, preferably 20 to 80% by weight, more preferably 20 to 70% by weight, of the active ingredient of the additive.

Composition Manufacturing Lubricating Oil Compositions can be made by adding an effective small amount of a mixture of at least one additive to an oil of lubricating viscosity, optionally with one or more auxiliary additives as described above. This process can be achieved by dispersing or dissolving the additives by adding them directly to the oil or by adding them in the form of their concentrates. Additives may be added to the oil by any method known to those skilled in the art prior to the addition of other additives, at the same time as the addition of other additives, or subsequent to the addition of other additives. it can.
The lubricating oil composition of the present invention can be used by adding lubricating oil to mechanical engine parts, particularly internal combustion engines such as compression ignition engines. A specific example of a compression ignition engine is one that has been developed in recent years and that allows the top ring groove temperature to exceed 150 ° C. because the specific power output increases to about 40 kW / liter or more. These engines tend to be damaged by the ring sticking problem when operating.

When the lubricating oil composition of the present invention is produced using the concentrate, it can be diluted with an oil having a lubricating viscosity of, for example, 3 to 100 parts by mass, for example 5 to 40 parts by mass, per 1 part by mass of the concentrate.
When the lubricating oil composition contains one or more additives, each additive is typically blended into the base oil in an amount that can impart the desired function to the lubricating oil composition. Representative effective amounts of such additives when used in crankcase lubricants are listed below. All values listed herein are indicated as mass% active ingredient unless otherwise stated.

Additive Mass% Mass%
(Wide range) (Preferred range)
Ashless dispersant 0.1-20 1-8
Metal detergent 0.1-6 0.2-4
Corrosion inhibitor 0-5 0-1.5
Dihydrocarbyl dithiophosphate metal 0.1-6 0.1-4
Additional antioxidants 0-5 0.01-1.5
Pour point depressant 0.01-5 0.01-1.5
Foam inhibitor 0-5 0.001-0.15
Additional antiwear agent 0-0.5 0-0.2
Friction modifier 0-5 0-1.5
Viscosity improver 0.01-6 0-4
Mineral oil base or synthetic base oil Balance Balance

  The final composition may contain 5 to 25% by weight, preferably 5 to 18% by weight, typically 10 to 15% by weight of the concentrate, the balance being an oil of lubricating viscosity.

The invention will now be described in detail by way of example:
Four additive packages (ie, “adpacks”) were produced by methods known in the art, and were packaged 1, A, 2, and B. In these packages, packages 1 and 2 contain molybdenum (same concentration), packages A and B do not contain molybdenum, packages 1 and A contain less amount of dispersant than packages 2 and B, The same except that 1 and A have the same dispersant concentration and packages 2 and B have the same dispersant concentration.
Each package contained the following additives at the same concentration;
Polybutene succinimide dispersant Overbased calcium sulfonate detergent Overbased magnesium sulfonate detergent Neutral calcium sulfonate detergent Neutral calcium phenate Hindered phenol antioxidant Ethoxylated amine friction modifier Glycerol monooleate friction modifier Zinc dialkyldithiophosphate antiwear agent Silicone foam inhibitor Demulsifier Diluted oil

Packages 1 and 2 contained trinuclear molybdenum / thiocarbamate sulfur. Package 1 and A contained less amount of dispersant than packages 2 and B.
Each package was blended into a Group IV basestock mixture to obtain a SAE-0W-30 lubricating oil composition (or oil) having the following properties. Each oil is indicated with the same reference number or letter as that blended from the package.

oil
1 A 2 B
Noack Volatile 10.7 10.6 11 10.6
Cl content (ppm) 26 26 26 26
Mo content (ppm) 100 0 100 0
Surfactant content (mmole / kg) 14.2 14.2 14.2 14.2
Dispersant content (mass%) 2.6 2.6 3.5 3.5

Test and Results Samples of each oil 1, A, 2, and B were subjected to the VWTDi CEC-L-78-T-97 test.
The results are listed in the table below.
oil
1 A 2 B
Merit 1 65 46 68 56
Ring ring 2 (average) 0 2.63 0 0.63
Ring fitting 3 (maximum) 0 5.0 0 2.5

Each test was operated at its maximum duration, i.e., without ending early.
1. The ACEA B4 limit is> 65.
2. The ACEA B4 limit is <0.7.
3. The ACEA B4 limit is <2.5.
The results clearly show the advantages of low concentrations of molybdenum in the test. Thus, by introducing them, oils that fail the test are converted into oils that easily pass the test both at high and low dispersant concentrations.

In a further embodiment of the invention, a trinuclear molybdenum / thiocarbamate sulfur additive, diphenyl-amine antioxidant (0.35 wt%) and a hindered phenol antioxidant (1. SAE 5W-30 lubricating oil composition (Oil 3) containing 1% by weight) was prepared. Oil 3 had other properties that the composition of the first aspect of the invention had.
Oil 3 was tested in the API Seq III test and was run at twice the specified time (128 hours versus 64 hours). Regulatory tests relate to piston cleanliness, cam and lifter wear, and increased viscosity in oil. By doubling the duration of the test, the severity was increased: under these conditions, viscosity increase is usually a limiting factor, and therefore control of oil viscosity by using additives is important.
The results obtained are as follows:

  Under the ACEA AI-98 (ASTM D 5533) specification for the Seq III E test, the oil viscosity increase at 40 ° C. should be ≦ 100%. Therefore, the above results show that the oil tested (oil 3) using a mixture of two different antioxidants shows significant performance in the harsh tests conducted as described above. ing.

Claims (12)

Noac volatility with CEC L-40-A-93 is less than 15% mass loss, eg less than 13% mass loss, preferably less than 11% mass loss, M-111 fuel economy according to CEC L-54-T-96 Is a SAE 0W-30 or 5W-30 or 5W-20 multigrade lubricating oil composition, which may contain 1.5% or more, and contains the following (A) to (E), or the following ( The composition produced by mixing A) to (E);
(A) 0 to 10% by weight of a Group I base stock or a Group II base stock or a mixture of a Group I and Group II base stock other than the base stock generated from the supply of additive components in the composition Less than, preferably less than 0 to 5% by weight of a base stock of a large amount of lubricating viscosity; and a small amount of additive components containing the following (B) to (E):
(B) one or more molybdenum-containing additives in an amount to provide elemental molybdenum in the composition at 1000 ppm by weight or less, preferably 500 ppm by weight or less, for example 250 ppm by weight or less;
(C) one or more calcium detergent additives containing as a surfactant a calcium salt of an organic acid in an amount providing 10 mmol or more, for example 12 mmol or more, of surfactant per kg of composition;
(D) One or more other lubricating oil additives selected from ashless dispersants, metal detergents, antioxidants, antiwear agents, and friction modifiers (provided that these additives are the above-mentioned (B) And (different from (C)); and (E) one or more viscosity modifiers.
(Here, these additive components provide the composition with less than 100 ppm by weight of chlorine, for example less than 50 ppm by weight.)   The composition of claim 1 which does not contain one or more secondary aromatic amine antioxidants.   The composition of claim 1 comprising a secondary aromatic amine antioxidant and a sterically hindered phenol antioxidant.   The composition according to any one of claims 1 to 3, wherein the component (D) contains one or more friction modifiers selected from esters of polyhydric alcohols and alkoxylated amines.   The component (C) is an overbased calcium salt of an organic acid, and the acid is phenol or sulfonic acid such that the surfactant is phenate or sulfonate. Composition.   The composition according to any one of claims 1 to 5, wherein the molybdenum-containing additive contains a molybdenum core and an oil-soluble molybdenum compound containing one or more ligands that impart oil solubility bound to the core.   The composition according to claim 6, wherein the molybdenum core is a dinuclear or trinuclear molybdenum core, or a combination thereof, and may contain nonmetallic atoms containing sulfur in whole or in part.   The composition according to claim 6 or 7, wherein the ligand is dialkyldithiocarbamate or dialkyldithiophosphate.   The composition according to any one of claims 1 to 8, further comprising a zinc dialkyldithiophosphate additive wherein the alkyl group is essentially a secondary alkyl group.   A method of lubricating a compression ignition internal combustion engine comprising operating the compression ignition internal combustion engine and lubricating the engine with the lubricating oil composition of any one of claims 1-9.   A method of reducing the ring sticking tendency of a compression ignition internal combustion engine comprising adding the lubricating oil composition according to any one of claims 1 to 9 to the compression ignition internal combustion engine.   A combination comprising a crankcase of a compression ignition internal combustion engine, preferably a crankcase having a specific output of 40 kW / liter or more, and the lubricating oil composition according to any one of claims 1-9.