JP2019173000A - Lubricant composition - Google Patents

Abstract

An object of the present invention is to further improve the friction and fuel economy performance of a lubricating oil for an automobile engine. The problem is solved by a lubricating oil composition for motor vehicles comprising the following components: (A) a base oil having a lubricating viscosity; (B) at least one benzotriazole derivative having a specific structure. (C) at least one molybdenum dithiocarbamate compound having a specific structure; and (D) a metal-containing or ashless detergent, ashless antioxidant, antiwear additive, corrosion inhibitor, rust inhibitor. One or more additional additives selected from viscosity index improvers, and dispersants, in the composition, the lubricating oil composition contains 100-2,000 ppm total molybdenum from component (C). And the benzotriazole derivative (B) is present in the lubricant in an amount of 0.001 to 5% by weight. [Selection diagram] None

Description

  The present invention relates to automotive engine lubricants that exhibit improved friction and fuel consumption reduction, particularly at lower operating temperatures, particularly at engine operating temperatures of 80 ° C. or lower.

It is well known that molybdenum-containing additives can be used in automotive engine lubricants for the purpose of improving friction reduction performance. However, it has generally been found that the effectiveness of such additives is not realized until the temperature of the engine reaches approximately 80 ° C. Therefore, when the engine is operated at a temperature of 80 ° C. or lower, the above-described excellent friction reducing characteristics of the molybdenum-containing additive are not exhibited.
Benzotriazole compounds have been used for many years in lubricating oil compositions as corrosion inhibitors to reduce copper corrosion.

  It is an object of the present invention to further improve the friction and fuel economy performance of automobile engine lubricants.

According to a first aspect, the present invention provides a lubricating oil composition for an automobile engine, the lubricating oil composition comprising the following components:
(A) Base oil with lubricating viscosity;
(B) at least one benzotriazole derivative represented by the following formula (I):

式(I)

Formula (I)

Wherein R ⁵ is a hydrocarbyl group having 1 to 3 carbon atoms, and R ⁶ is a tertiary amino group represented by the following formula:

Wherein R ⁷ and R ⁸ are independently linear or branched hydrocarbyl groups having 3 to 10 carbon atoms;
(C) at least one molybdenum dithiocarbamate compound represented by any of the following formulas (II) or (III):

式(II)

Formula (II)

In which R _{1 to} R ₄ independently represent a linear, branched or aromatic hydrocarbyl group having 1 to 24 carbon atoms, and X _{1 to} X ₄ independently represent an oxygen atom or a sulfur atom. Means
Mo ₃ S _k L _n Q _z formula (III)
Wherein L is an independently selected ligand comprising an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, and n is 1-4 , K is 4-7, Q is selected from the group consisting of neutral electron donating compounds such as water, amines, alcohols, phosphines and ethers, and z is in the range of 0-5, and non Including stoichiometric values; and
(D) One or more additional additives selected from metal-containing or ashless detergents, ashless antioxidants, antiwear additives, corrosion inhibitors, rust inhibitors, viscosity index improvers and dispersants Agent,
Including
Wherein, the lubricating oil composition contains 100 to 2,000 ppm of molybdenum derived from component (C) in total, and the benzotriazole derivative (B) is contained in the lubricating oil in an amount of 0.001 to 5% by mass. Exists.
Preferably, the base oil (A) having the lubricating viscosity is present in a large amount.
Preferably, the automobile engine lubricating oil composition of the present invention is used to lubricate a crankcase of the engine (that is, a lubricant for a crankcase of an automobile engine).

Suitably, the automotive engine lubricating oil composition is used for the purpose of lubricating automotive spark ignition or automotive compression ignition internal combustion engines, preferably automotive spark ignition internal combustion engines.
Unexpectedly, the use of the above benzotriazole compound as an additive in a lubricating oil composition comprising a molybdenum-containing additive, particularly a molybdenum dithiocarbamate compound, is intended for the lubricating oil composition to lubricate automotive engines. It has been found that, when used, it is possible to achieve an improvement in the friction reduction performance, particularly the boundary regime friction reduction performance, of the molybdenum-containing additive. Moreover, the improved friction reduction performance of the molybdenum-containing compound is realized at lower engine operating temperatures, i.e., when the engine is operating at temperatures below 80 ° C. Accordingly, the automotive engine lubricating oil composition of the present invention provides advantages with respect to improved friction reduction and / or improved fuel consumption reduction.
According to a second aspect, the present invention provides a method for lubricating an automobile engine, said method comprising a lubricating oil composition as defined according to the first aspect of the present invention above, Including a step of lubricating. Suitably, the method of the present invention comprises the step of lubricating the engine crankcase.
According to a third aspect, the present invention relates to the lubrication of an automobile engine, the base oil (A) having a lubricating viscosity as defined in the first aspect of the present invention and at least one molybdenum dithiol. A lubricating oil composition containing a carbamate compound (C) in an effective minor amount to improve the friction reducing performance characteristics of the molybdenum dithiocarbamate compound (s) (C) during operation of the automobile engine. There is provided the use of at least one benzotriazole derivative (B) as defined in the first aspect of the invention as an additive, wherein the molybdenum dithiocarbamate compound (s) (C) Provides 100 to 2,000 ppm of molybdenum to the lubricating oil composition.

According to a fourth aspect, the present invention relates to at least one benzotriazole derivative (B), as defined in the first aspect of the present invention, and An effective minor combination of additives in a lubricating oil composition containing a base oil (A) having a lubricating viscosity in combination with at least one molybdenum dithiocarbamate compound (C) as defined in one aspect. Wherein the molybdenum dithiocarbamate compound (s) (C) is used to improve friction reduction of the lubricating oil composition during operation of the automobile engine as The lubricating oil composition is provided with 100 to 2,000 ppm of molybdenum.
According to a fifth aspect, the present invention relates to at least one benzotriazole derivative (B), as defined in the first aspect of the present invention, and An effective minor additive in a lubricating oil composition comprising a base oil (A) having a lubricating viscosity in combination with at least one molybdenum dithiocarbamate compound (C) as defined in the first aspect As a combination of, to reduce the fuel consumption of the engine during operation of the automobile engine, wherein the molybdenum dithiocarbamate compound (s) (C) The composition is provided with 100-2,000 ppm molybdenum.
Preferably, the automobile engine according to the second to fifth aspects of the present invention operates at a temperature of 80 ° C. or lower.
Preferably, the lubricating oil composition as defined in the third, fourth and fifth aspects of the present invention comprises (D) a metal-containing or ashless detergent, an ashless antioxidant, an abrasion It further comprises one or more additional additives selected from prevention additives, corrosion inhibitors, rust inhibitors, viscosity index improvers and dispersants.
Suitably, the engine as defined in the second, third, fourth and fifth aspects of the invention is a spark ignition or compression ignition internal combustion engine, preferably a spark ignition internal combustion engine. .

Suitably, the at least one benzotriazole derivative (B) is a lubricating oil composition according to the first aspect of the invention and a lubricating oil as defined in the second to fifth aspects of the invention. In the composition, in an amount of 0.001 to 5% by weight, preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, even more preferably 0.01 to 0.04% by weight based on the active matter. % Present.
Suitably, the at least one molybdenum dithiocarbamate compound (C) is a lubricating oil composition according to the first aspect of the invention and a lubrication as defined in the second to fifth aspects of the invention. In the oil composition, a total amount of 100 to 2,000 ppm, preferably 450 to 2,000 ppm, more preferably 450 to 1,200 ppm, even more preferably 450 to 900 ppm, most preferably 600 to 900 ppm of molybdenum (ASTM D5185) is provided. .
Suitably, the lubricating oil composition according to the present invention has a sulfated ash content (ASTM of 1.2 mass% or less, preferably 1.1 mass% or less, more preferably 1.0 mass% or less, based on the total mass of the composition). D874).
Preferably, the lubricating oil composition according to the present invention comprises low levels of phosphorus. Suitably, the lubricating oil composition is 0.12 wt% or less, preferably up to 0.11 wt%, more preferably 0.10 wt% or less, even more preferably 0.09 wt% or less, based on the total weight of the composition More preferably, it contains phosphorus in an amount of 0.08 wt% or less, most preferably 0.06 wt% or less of phosphorus (ASTM D5185). Suitably, the lubricating oil composition comprises 0.01% by weight or more, preferably 0.02% by weight or more, more preferably 0.03% by weight or more, and even more preferably 0.05% by weight or more phosphorus based on the total weight of the composition. In this amount, phosphorus is included.

Typically, the lubricating oil composition can contain low levels of sulfur. Preferably, the lubricating oil composition is in an amount of up to 0.4 wt%, more preferably up to 0.3 wt%, even more preferably up to 0.2 wt% sulfur (ASTM D2622), based on the total weight of the composition. Contains sulfur.
Typically, one lubricating oil composition according to the present invention is up to 0.30% by weight, more preferably up to 0.20% by weight, based on the total weight of the composition and as measured according to ASTM method D5291. Most preferably, it contains up to 0.15% by weight of nitrogen.
Suitably, the lubricating oil composition may have a total base number (TBN) as measured according to ASTM D2896 of 4-15 mg KOH / g, preferably 5-12 mg KOH / g.
As used herein, the following terms and expressions, if used, have the meanings given below:
“Active ingredients” or “(ai)” means an additive material that is not a diluent or solvent;
The term “comprising” or any synonymous terms specifies the presence of a stated feature, step, or integer or component, but one or more other features, steps, integers, components or groups of these It does not exclude the presence or addition. The expression `` consists of '' or `` consists essentially of '' or the expression of a synonym can be included within the scope of `` comprises '' or the term of the same Where “consisting essentially of” makes it possible to include a substance that does not substantially affect the characteristics of the composition to which it is applied;

“Hydrocarbyl” means a chemical group of a compound that contains hydrogen and carbon atoms and is directly bonded to the remainder of the compound via a single carbon atom. The group may contain one or more atoms other than carbon and hydrogen, provided that these atoms do not affect the essential hydrocarbyl properties of the group. Those skilled in the art will recognize suitable groups (eg, halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkyl mercapto, nitro, nitroso, sulfoxy, etc.). Preferably, the group consists essentially of hydrogen and carbon atoms, unless otherwise specified. Preferably, the hydrocarbyl group comprises an aliphatic hydrocarbyl group. The term “hydrocarbyl” includes “alkyl”, “alkenyl”, “allyl” and “aryl” as defined herein.
“Alkyl” means a C ₁ -C ₃₀ alkyl group that is bonded directly to the remainder of the compound through a single carbon atom. Unless otherwise specified, an alkyl group can be linear (i.e., unbranched) or branched and can be cyclic, acyclic or partially cyclic / non-cyclic when there are a sufficient number of carbon atoms. It can be cyclic. Preferably, the alkyl group comprises a linear or branched acyclic alkyl group. Representative examples of alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, Xyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl;

“Aryl” is a C ₆ -C ₁₈ , preferably C ₆ -C ₁₀ aromatic group, optionally substituted by one or more alkyl groups, halo, hydroxyl, alkoxy and amino groups, the compound The aromatic group bonded directly to the remainder of the group via a single carbon atom. Preferred aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, especially phenyl and alkyl substituted derivatives thereof;
“Alkenyl” is a C ₂ containing at least one carbon-carbon double bond and directly attached to the remainder of the compound via a single carbon atom, and otherwise defined as “alkyl”. -C _30, preferably refers to the group C ₂ -C _12;
“Alkylene” means a C ₂ -C ₂₀ , preferably C ₂ -C ₁₀ , more preferably C ₂ -C ₆ divalent saturated acyclic aliphatic group that may be linear or branched. . Representative examples of alkylene are ethylene, propylene, butylene, isobutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1- Including dimethylethylene and 1-ethylpropylene;
“Polyol” means an alcohol containing two or more hydroxyl functions (ie, a polyhydric alcohol), but is used to form the oil-soluble or oil-dispersible polymeric friction modifiers described above. “Polyalkylene glycol” (component B (ii)) is excluded. More specifically, the term “polyol” includes diols, triols, tetraols and / or related dimer or chain extended polymers of such compounds. Even more specifically, the term “polyol” includes glycerol, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol;

“Polycarboxylic acid” means an organic acid containing two or more carboxylic acid functional groups, preferably hydrocarbyl acid. The term “polycarboxylic acid” includes di-, tri- and tetra-carboxylic acids;
“Halo” or “halogen” includes fluoro, chloro, bromo and iodo;
As used herein, the term “oil-soluble” or “oil-dispersible” or synonymous terms means that the compound or additive is in any proportion to the oil. It does not necessarily indicate that it is soluble, soluble, miscible or can be suspended. However, these indicate that the compound or additive is soluble or stable in the oil to the extent that it is sufficient to exert their intended effect, for example, in the environment in which the oil is used. It certainly means that it can be dispersed. Moreover, additional incorporation of other additives may also allow higher levels of incorporation of special additives if necessary;
“Ashless” in reference to an additive means that the additive does not contain a metal;
“Ash-containing” in relation to an additive means that the additive contains a metal;
A “major amount” is calculated as the active ingredient associated with a stated component of a composition, expressed in relation to that component and relative to the total mass of the composition. Means over 50% by weight of
“Minor amount” is calculated as the active ingredient for a stated additive of a composition, expressed in terms of the additive and in terms of the total mass of the composition. Means less than 50% by weight;

“Effective minor amount” in relation to an additive means the amount of the additive in a lubricating oil composition such that such additive provides the desired technical effect. ;
“Ppm” means parts per million by weight, based on the total weight of the lubricating oil composition;
The “metal content” of the lubricating oil composition or additive component, such as detergent metal, molybdenum or boron content or the total metal content of the lubricating oil composition (ie, all individual metals) Total content) is measured according to ASTM D5185;
“TBN” in relation to the additive component or lubricating oil composition of the present invention means total base number (mg KOH / g) as measured by ASTM D2896;
“KV ₁₀₀ ” means kinematic viscosity at 100 ° C. as measured by ASTM D445;
“Phosphorus content” is measured by ASTM D5185;
“Sulfur content” is measured by ASTM D2622; and “Sulfate ash content” is measured by ASTM D874.
All reported percentages are by weight, unless stated otherwise, based on the active ingredient, i.e. not considering carrier or diluted oil.
Similarly, the essential and optimal and customary ingredients used may react under the conditions of formulation, storage and use, and the present invention will It will also be understood that it also provides a product that can be obtained or obtained as a result of such a reaction.
Further, it is understood that any upper and lower limits in the amounts, ranges and ratios described herein can be combined independently.
Similarly, it will be understood that preferred features according to each aspect of the invention are considered preferred features according to all other aspects of the invention.

Oils with a lubricating viscosity Oils with the above-mentioned lubricating viscosity (often referred to as `` base stock '' or `` base oil '') are the main liquid components of a lubricant, in which additives and Other oils are possibly blended to provide the final lubricant (or lubricating composition), for example. Base oils are useful for making concentrates and for making lubricating oil compositions therefrom, and can be selected from natural (plant, animal or mineral) and synthetic lubricating oils and mixtures thereof.
The above-mentioned base stock group is a publication of American Petroleum Institute (API): “Engine Oil Licensing and Certification System”, Industry Services Department, 14th. Edition, December 1996, Addendum 1, December 1998. Typically, the base stock has a viscosity at 100 ° C. of preferably 3-12 mm ² / s (cSt), more preferably 4-10 mm ² / s, most preferably 4.5-8 mm ² / s. I will.
The definitions of the above base stock and base oil in the present invention are the publications of the American Petroleum Institute (API): “Engine Oil Licensing and Certification System”, Industrial Services (Industry). Services Department), 14th edition, December 1996, Addendum 1, December 1998. This publication classifies the base stock as follows:
a) Group I base stock contains less than 90% saturates and / or more than 0.03% sulfur and using the test methods specified in Table E-1 below And a viscosity index of 80 or more and less than 120.
b) Group II base stock contains 90% or more of saturates and 0.03% or less of sulfur, and 80 or more when using the test method specified in Table E-1 below. And has a viscosity index of less than 120.
c) Group III base stock contains not less than 90% saturates and not more than 0.03% sulfur, and not less than 120 when using the test methods specified in Table E-1 below. Has a viscosity index.
d) Group IV base stock is poly α-olefin (PAO).
e) Group V base stock includes all other base stocks not included in Group I, II, III or IV.

Other oils with lubricating viscosity that can be included in the lubricating oil composition of the present invention are described in detail as follows:
Natural oils include animal and vegetable oils (eg, castor oil and lard oil), liquid petroleum oils and hydrorefined, solvent-treated, mineral-based lubricating oils of the paraffin, naphthene and mixed paraffin-naphthene type. Oils with a lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils are hydrocarbon oils such as polymerized and copolymerized olefins (e.g. polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly (1-hexene), poly (1-octene), poly (1- 1-decene)); alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenols (eg, biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkyls Diphenyl sulfide and derivatives, analogs and homologues thereof.
Another suitable class of synthetic lubricants are dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid. Esters of dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Including. Specific examples of these esters are dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl Sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid.

Similarly, Esters useful as synthetic oils and C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers such as those prepared from neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol including.
Unrefined, refined and re-refined oils can be used in the above compositions of the present invention. Unrefined oil is oil obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly from retorting operations, petroleum oil obtained directly by distillation or ester oil obtained directly by an esterification process and used without further treatment is unrefined oil. Let's go. Refined oils are similar to the unrefined oils except that they are further processed in one or more purification steps with the aim of improving one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. The rerefined oil is obtained by a method similar to that used to obtain the refined oil, which is applied to the refined oil already used in operation. Such rerefined oils are also referred to as reclaimed oils or reprocessed oils and are often additionally processed by techniques for approval with respect to used additives and oil breakdown products.

Other examples of base oil are gas - Two - a Liquid (gas-to-liquid) ( "GTL") base oils, i.e. the base oil, Fischer - Tropsch (Fischer-Tropsch) with a catalyst, H ₂ and CO It may also be a Fischer-Tropsch synthesized hydrocarbon-derived oil produced from a synthesis gas containing Typically, these hydrocarbons require further processing in order to be useful as a base oil. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art.
Preferably, the oil having the lubricating viscosity is present in an amount exceeding 55% by weight, more preferably exceeding 60% by weight, even more preferably exceeding 70% by weight, based on the total weight of the lubricating oil composition. To do. Preferably, the oil having the lubricating viscosity is present in an amount of less than 98% by weight, more preferably less than 95% by weight, and even more preferably less than 90% by weight, based on the total weight of the lubricating oil composition.
The lubricating oil composition according to each aspect of the present invention may be a multigrade oil identified by viscosity descriptors SAE 20W-X, SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X. Thus, X represents any one of 8, 12, 16, 20, 30, 40 and 50, and the characteristics relating to the different viscosity grades can be found in the SAE J300 classification. In one embodiment according to each aspect of the present invention, independently of the other embodiments, the lubricating oil composition is in the form of SAE 10W-X, SAE 5W-X or SAE 0W-X viscosity grade, preferably SAE 0W. In the form of -X or SAE 5W-X viscosity grade, where X represents any one of 8, 12, 16, 20 or 30. Preferably X is 8, 12, 16 or 20.

Benzotriazole derivative (B)
The lubricating oil composition of the present invention comprises at least one benzotriazole derivative represented by the following formula (I):

式(I)

Formula (I)

Wherein R ⁵ is a hydrocarbyl group containing 1 to 3 carbon atoms and R ⁶ is a tertiary amino group represented by the following formula:

Wherein R ⁷ and R ⁸ are independently linear or branched hydrocarbyl groups having 3 to 10 carbon atoms.
In a preferred embodiment, R ⁵ is a methyl group. Preferably R ⁷ and R ⁸ are both the same. In a preferred embodiment, R ⁷ and R ⁸ are hydrocarbyl groups having 6-8 carbon atoms.
In a preferred embodiment, the benzotriazole derivative has the following structure:

  Suitably, the benzotriazole derivative is present in the lubricating oil composition of the present invention in an amount of 0.001-5% by weight, preferably 0.01-2% by weight, for example 0.01-1% by weight, based on the active substance. It exists in the quantity. In a preferred embodiment, the benzotriazole derivative is present in the lubricating oil composition of the present invention in an amount of 0.01-0.04% by weight based on the active substance.

Oil-soluble molybdenum compound (C)
Suitable dinuclear or dimeric molybdenum dialkyldithiocarbamate compounds are represented by the following formula (II):

Wherein R _{1 to} R ₄ independently represent a linear, branched or aromatic hydrocarbyl group having 1 to 24 carbon atoms; and X _{1 to} X ₄ independently represent an oxygen atom or a sulfur atom To do. The four hydrocarbyl groups, R _{1 to} R ₄ , may be different from each other or the same.
Suitable trinuclear organomolybdenum compounds include molybdenum compounds having the formula: Mo ₃ S _k L _n Q _z and mixtures thereof, where L is sufficient to render the compound soluble or dispersible in the oil. Is an independently selected ligand containing an organic group with any number of carbon atoms, n is 1 to 4, k varies from 4 to 7, Q is water, amine, alcohol, phosphine and ether, etc. Selected from the group consisting of neutral electron donating compounds, and z is in the range of 0-5 and includes non-stoichiometric values. At least 21 carbon atoms, for example at least 25, at least 30 or at least 35 carbon atoms should be present in the organic group of all the ligands.
The ligand is independently selected from the following groups and mixtures thereof:

Thus, X, X ₁ , X ₂ and Y are independently selected from the group consisting of oxygen and sulfur, and wherein R ₁ , R ₂ and R are independently selected from hydrogen and organic groups, which may be the same May be different. Preferably, the organic group is a hydrocarbyl group, such as an alkyl (eg, the carbon atom bonded to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
Importantly, the organic group of the ligand has a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil. For example, the number of carbon atoms in each group will generally range from about 1 to about 100, preferably from about 1 to about 30, and more preferably from about 4 to about 20. Preferred ligands include dialkyldithiophosphates, alkylxanthates, and dialkyldithiocarbamates, and of these, dialkyldithiocarbamates are more preferred. Organic ligands containing two or more of the above functional groups can also function as ligands and can bind to two or more of the cores. One skilled in the art will recognize that the formation of the compounds of the present invention requires the selection of a ligand with a suitable charge to offset the core charge.
A compound having the above formula: Mo ₃ S _k L _n Q _z has a cationic core surrounded by an anionic ligand and is represented, for example, by the following structure and has a net charge of +4:

and

As a result, in order to solubilize these cores, the total charge on all of the ligands must be -4. Four monoanionic ligands are preferred. While not intending to be bound by any theory, two or more trinuclear cores can be bound or interconnected by one or more ligands and the ligands can be multidentate It seems to be. This includes the case of multidentate ligands with multiple bonds to a single core. It is believed that oxygen and / or selenium can replace sulfur in the core (s).
Oil-soluble or oil-dispersible trinuclear molybdenum compounds can be prepared in suitable liquid (s) / solvent (s) such as (NH ₄ ) ₂ Mo ₃ S ₁₃ .n (H ₂ O) Can be prepared by reacting a molybdenum source with a suitable ligand source, such as tetraalkylthiuram disulfide, where n varies between 0 and 2 and is non-stoichiometric. Contains a value. Other oil-soluble or oil-dispersible trinuclear molybdenum compounds can be obtained from a molybdenum source such as (NH ₄ ) ₂ Mo ₃ S ₁₃ .n (H ₂ O), tetra It can be formed during the reaction of a ligand source such as alkyl thiuram disulfide, dialkyl dithiocarbamate or dialkyl dithiophosphate and a sulfur abstraction agent such as cyanide ion, sulfite ion or substituted phosphine. Alternatively, a trinuclear molybdenum-sulfur halide salt such as [M '] ₂ [Mo ₃ S ₇ A ₆ ] (where M' is a counter ion and A is a halogen such as Cl, Br or I). A ligand source, such as a dialkyldithiocarbamate or dialkyldithiophosphate, to form an oil-soluble or dispersible trinuclear molybdenum compound in the appropriate liquid (s) / solvent (s) Can be reacted. The suitable liquid / solvent can be, for example, aqueous or organic.
The oil-solubility or dispersibility of a compound can be influenced by the number of carbon atoms in the organic group of the ligand. Preferably, at least 21 total carbon atoms should be present in the organic group of all the ligands. Preferably, the selected ligand source contains a sufficient number of carbon atoms in its organic group to render the compound soluble or dispersible in the lubricating oil composition.
The lubricating oil composition of the present invention can contain either a dimer-type or trimmer-type molybdenum compound or both.

The total amount of oil soluble molybdenum dithiocarbamate compound will depend on the specific performance requirements of the lubricating oil composition. Suitably, the lubricating oil composition according to the present invention provides the composition with at least 100 ppm, or at least 200 ppm, or at least 300 ppm, or at least 400 ppm, or at least 450 ppm molybdenum (as measured according to ASTM D5185). Inclusive of the total amount of molybdenum dithiocarbamate compound. The lubricating oil composition according to all aspects of the invention comprises the molybdenum compound in the composition up to 2,000 ppm, or up to 1,500 ppm, or up to 1,200 ppm, or up to 800 ppm molybdenum (according to ASTM D5185). Can be included in an amount to give (as measured). In a preferred embodiment, the molybdenum dithiocarbamate compound (C) provides 600 to 900 ppm of molybdenum to the lubricating oil composition.
Preferably, the dimer-type molybdenum dithiocarbamate and / or the trimer-type molybdenum dithiocarbamate is the only source of molybdenum atoms in the lubricating oil composition.
In a preferred embodiment, the lubricating oil composition comprises both dimer-type and trimer-type oil-soluble molybdenum dithiocarbamates.

Additional additive (D)
Similarly, the lubricating oil according to all aspects of the present invention may contain one or more additional conventional additives, the additional conventional additives being metal-containing or ashless detergent, ashless oxidation Including, but not limited to, inhibitors, antiwear additives, corrosion inhibitors, rust inhibitors, viscosity index improvers and dispersants.
Amine-based friction modifier: In a preferred embodiment, the lubricating oil composition of the present invention comprises an amine-based friction modifier having a structure according to the following formula (IV):

式(IV)

Formula (IV)

Typically, the total amount of the amine friction modifier represented by formula (IV) in the lubricating oil composition according to all aspects of the present invention is 5% by weight based on the total weight of the lubricating oil composition. Does not exceed, and preferably does not exceed 2% by weight, and more preferably does not exceed 0.5% by weight. Preferably, the amine friction modifier having the formula (IV) is 0.1 to 1.0% by weight, more preferably 0.1 to 0.5% by weight, and still more preferably in the lubricating oil composition according to all aspects of the present invention. It is present in an amount of 0.1 to 0.3% by weight.
Dispersant: This is an additive whose main function is to keep solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits while at the same time depositing sludge Is to reduce. For example, the dispersant keeps oil-insoluble materials resulting from oxidation during use of the lubricant in suspension, thus preventing sludge agglomeration and precipitation or deposition on metal parts of the engine.
Dispersants are non-metallic organic materials that are usually “ashless” and contain virtually no ash upon combustion, in contrast to materials that contain metals and thus form ash. These include long hydrocarbon chains with a polar head, the polarity being derived from including, for example, O, P or N atoms. The hydrocarbon is an oleophilic group imparting oil-solubility, for example containing 40 to 500 carbon atoms. Thus, the ashless dispersant can include an oil-soluble polymer backbone.
The ashless dispersant suitable for all aspects of the invention is preferably an ashless nitrogen-containing dispersant.
Suitable ashless dispersants can be made from functionalized polyalkenes by a thermal “ene” reaction, which is a known reaction exclusively. Such polyalkenes are, for example, a mixture mainly comprising at least 65%, such as 70%, more preferably at least 85% terminal vinylidene groups. One example is the polyalkene known as highly reactive polyisobutene (HR-PIB), which is commercially available under the trade name Glissopal ^™ (formerly BASF). . US-A-4,152,499 describes the production of such polymers.

Alternatively, the ashless dispersant can be made from a polyalkene that has been functionalized by the so-called chlorination method, which produces a small percentage of the polymer chains (eg, less than 20%) having terminal vinylidene groups. Give things.
Preferred monounsaturated reactants that can be used to functionalize the polyalkene include mono- and di-carboxylic acid materials, i.e., acid, anhydride or acid ester materials, and (i) monounsaturated C a ₄ -C ₁₀ dicarboxylic acid, where (a) the carboxyl groups are vicinyl (i.e., adjacent located on the carbon atom) at least one of and (b) said adjacent carbon atoms, preferably both has become a part of the monounsaturated, the monounsaturated carboxylic acid; anhydrides or C ₁ -C ₅ alcohol derived mono (ii) (i) a derivative of, for example, (i) - or di - An ester; (iii) a monounsaturated C ₃ -C ₁₀ monocarboxylic acid, wherein the carbon-carbon double bond is conjugated to the carboxyl group, ie having the structure —C═C—CO— Monounsaturated carboxylic acids; and (iv) derivatives of (iii), such as C ₁ -C of (iii) ₅ Contains mono- or di-esters derived from alcohol. Mixtures of monounsaturated carboxylic acid materials (i)-(iv) can also be used. Upon reaction with the polyalkene, the unsaturation of the monounsaturated carboxylic reactant is saturated. Thus, for example, maleic anhydride becomes a polyalkene-substituted succinic anhydride and acrylic acid becomes a polyalkene-substituted propionic acid. Typical examples of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyls of the above (e.g., C ₁ -C ₄ alkyl) esters, such as methyl maleate, ethyl fumarate, and methyl fumarate.
In order to provide the required functionality, typically the monounsaturated carboxylic reactant, preferably maleic anhydride, is equimolar to 100% by weight excess, preferably 5 based on the number of moles of polyalkene. It will be used in amounts ranging from ˜50% by weight excess. Unreacted excess monounsaturated carboxylic reactant can be removed from the final dispersant product if necessary, for example by stripping, usually performed under reduced pressure.

  The functionalized oil-soluble polyalkene is then derivatized with a nucleophile such as an amine, amino alcohol, alcohol or mixtures thereof to form the corresponding derivative containing the dispersant. Amine compounds useful for derivatizing the functionalized polymer contain at least one amine and can contain one or more additional amino groups or other reactive or polar groups. These amines may be hydrocarbyl amines or may be exclusively hydrocarbyl amines, where the hydrocarbyl group may contain other groups such as hydroxy groups, alkoxy groups, amide groups, nitriles and imidazoline groups. . Particularly useful amine compounds include mono- and poly-amines, such as 1 to 12, for example 3 to 12, preferably 3 to 9, most preferably 6 to 7 nitrogen atoms per molecule, 2 to Includes polyalkenes and polyoxyalkylene polyamines having 60, for example 2 to 40 (eg, 3 to 20) total carbon atoms. Mixtures of amine compounds can be used advantageously. Preferred amines include aliphatic saturated amines including, for example, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; polyethylene amines such as diethylenetriamine, triethylenetetramine, tetra Ethylenepentamine; and polypropyleneamines such as 1,2-propylenediamine and di (1,2-propylene) triamine. Such polyamine mixtures known as PAM are commercially available. Particularly preferred polyamine mixtures are those derived by distilling light ends from the PAM product. This resulting mixture, known as “heavy” PAM or HPAM, is also commercially available. Properties and attributes relating to both PAM and / or HPAM include, for example, U.S. Pat. Nos. 4,938,881; 4,927,551; 5,230,714; 5,241,003; 5,565,128; 5,756,431; And in US Pat. No. 5,854,186.

Other useful amine compounds include alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane and heterocyclic nitrogen-based compounds such as imidazoline. Another useful class of amines are polyamides and related amide-amines such as those described in US Pat. Nos. 4,857,217; 4,956,107; 4,963,275; and 5,229,022. Also useful are tris (hydroxymethyl) aminomethane (TAM) as described in 4,102,798; 4,113,639; 4,116,876; and UK 989,409. Dendrimers, star amines, and amines with comb structures can also be used. Similarly, it is possible to use condensed amines as described in US Pat. No. 5,053,152. The functionalized polymer is reacted with the amine compound using conventional techniques such as those described, for example, in US Pat. Nos. 4,234,435 and 5,229,022, and in EP-A-208,560.
The dispersant of the present invention preferably comprises at least one dispersant, which is derived from a polyalkenyl-substituted mono- or di-carboxylic acid, anhydride or ester, per polyalkenyl moiety. It contains from 1.3 to 1.7, preferably more than 1.3 to 1.6, most preferably more than 1.3 to 1.5 functional groups (mono- or di-carboxylic acid generating moieties) (moderately functional dispersants). The functionality (F) can be determined according to the following formula:
F = (SAP x M _n ) / ((112,200 x AI)-(SAP x MW)) (1)
Thus, SAP is the saponification number (ie, milligrams of KOH consumed in completely neutralizing acid groups in 1 g of succinic acid-containing reaction product as determined according to ASTM D94); The number average molecular weight of the starting olefin polymer; AI is the proportion of active ingredient in the succinic acid-containing reaction product (the remainder being unreacted olefin polymer, succinic anhydride and diluent); And MW is the molecular weight associated with the mono- or di-carboxylic acid generating moiety (eg 98 for maleic anhydride).

In general, each mono- or di-carboxylic acid-generating moiety will react with a nucleophilic group (polar part of an amine, alcohol, amide or ester) and in the polyalkenyl-substituted carboxylic acylating agent. The number of functional groups will determine the number of nucleophilic groups in the finished dispersant.
The polyalkenyl moiety according to the dispersant of the present invention is at least 900, suitably at least 1,500, preferably between 1,800 and 3,000, such as between 2,000 and 2,800, more preferably between about 2,100 and 2,500 and Most preferably, it can have a number average molecular weight between about 2,200 and about 2,400. The molecular weight of the dispersant is generally represented by the molecular weight of the polyalkylene moiety, which means that the exact molecular weight range of the dispersant is the type of polymer used to derive the dispersant, the functional group This depends on a number of parameters including the number of nucleophiles and the type of nucleophilic group used.
The molecular weight of the polymer, specifically the following can be measured by various known techniques:

One convenient method is gel permeation chromatography (GPC), which additionally provides information on molecular weight distribution (WW Yau, JJ Kirkland & DD Bly, `` Modern Size Exclusion Liquid Chromatography (Modern Size Exclusion) Liquid Chromatography ”, John Wiley and Sons, New York, 1979). Another useful method for measuring molecular weight, particularly for lower molecular weight polymers, is the vapor pressure osmometry (see, eg, ASTM D3592).
Preferably, the polyalkenyl moiety in the dispersant of the present invention has a narrow molecular weight distribution (MWD), also called polydispersity, as determined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). . Most desirable are polymers with Mw / Mn of less than 2.2, preferably less than 2.0. Suitable polymers have a polydispersity of about 1.5 to 2.1, preferably about 1.6 to about 1.8.
Suitable polyalkenes used in the formation of the dispersants according to the invention include homopolymers, copolymers or low molecular weight hydrocarbons. One group of such polymers includes polymers of ethylene and / or C ₃ -C ₂₈ α-olefins having at least one formula H ₂ C═CHR ¹ , wherein R ¹ is ¹ to 26 Linear or branched alkyl groups containing carbon atoms, where the polymer contains carbon-carbon unsaturation and a high degree of terminal ethenylidene unsaturation. Preferably, such a polymer comprises a copolymer of ethylene and at least one α-olefin having the above formula, wherein R ¹ is alkyl having ¹ to 18 carbon atoms, and more preferably. Is an alkyl having 1 to 8 carbon atoms and more preferably 1 to 2 carbon atoms.

Another useful class of polymers is polymers made by cationic polymerization of monomers such as isobutene and styrene. Typical polymers from this class are polyisobutenes obtained by polymerization of the C ₄ refinery stream having a butene content of 35-75% by weight and an isobutene content of 30-60% by weight by the thermal “ene” reaction. including. A preferred monomer source for producing poly-n-butene is a petroleum feed stream such as Raffinate II. These feed streams are disclosed in the art, such as in US Pat. No. 4,952,739. In a preferred embodiment, polyisobutylene produced from a pure isobutylene stream or a Raffinate I stream is used to produce a reactive isobutylene polymer with terminal vinylidene olefins as described above.
The dispersant (s) of the present invention are preferably mono- or bis-succinimides.
The dispersant (s) of the present invention can generally be borated by conventional means such as taught in U.S. Pat.Nos. 3,087,936, 3,254,025, and 5,430,105. it can. Boration of the dispersant is an amount of boron oxide sufficient to give the acyl nitrogen-containing dispersant a 0.1-20 atomic ratio of boron for each mole of acylated nitrogen composition. , Easily achieved by treatment with boron compounds such as boron halides, boronic acids and esters of boronic acids.
Boron appearing in the product as a dehydrated boric acid polymer (mainly (HBO ₂ ) ₃ ) is bound to the imide and diimide of the dispersant, for example, as an amine salt, such as the metaborate of the diimide I think that the. Boronation is performed by adding a sufficient amount of a boron compound, preferably boric acid, usually as a slurry, to the acyl nitrogen-based compound and stirring at 135-190 ° C., for example, 140-170 ° C. for 1-5. This can be done by heating for a period of time followed by a nitrogen stripping treatment. Alternatively, the boron treatment can be performed by adding boric acid to the high temperature reaction mixture of the dicarboxylic acid material and amine and simultaneously removing water. Other post reaction steps known in the art can also be applied.

Typically, the lubricating oil composition of the present invention may comprise 1 to 20% by weight, such as 1 to 15%, preferably 1 to 10%, more preferably 2 to 5% by weight of a dispersant. .
In a preferred embodiment, the lubricating oil composition of the present invention contains 200 to 500 ppm of boron derived from a borated dispersant.
Metal-containing detergent: This functions as both a detergent and acid neutralizer or rust inhibitor to reduce or remove deposits, thereby reducing wear and corrosion and extending engine life. Detergents typically include a polar head with a long hydrophobic tail, which includes a metal salt of an acidic organic compound. These salts contain a substantially stoichiometric amount of the metal, in which case they are usually described as normal or neutral salts and typically have a total base number of 0-80 mg KOH / g. Or will have a TBN (as measured by ASTM D2896). Large amounts of metal base can be incorporated by reaction of an excess amount of metal compound (eg, oxide or hydroxide) with an acidic gas (eg, carbon dioxide). The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (eg, carbonate) micelle. Such overbased detergents can have a TBN of 150 mg KOH / g or more, and typically will have a TBN of 250-450 mg KOH / g or more. In the presence of the above compounds having Formula I, the amount of overbased detergent can be reduced, or detergents that are overbased at low levels (e.g., wash with 100-200 mg KOH / g TBN) Agent) or neutral detergents can be used, resulting in a corresponding decrease in the SASH content of the lubricating oil composition without degrading the performance of the lubricating oil composition.
Suitably, the lubricating oil composition of the present invention further comprises at least one metal-containing detergent additive.

The cleaning agents that can be used are oil-soluble, neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates of metals, in particular alkali or alkaline earth metals such as sodium, potassium, lithium, calcium and magnesium. , And naphthenates and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium, both of which can be present in the detergent used in the lubricating oil composition according to any aspect of the present invention. A combination of detergents can be used, either overbased, neutral, or both.
Sulfonates can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained by fractionation of petroleum or by alkylation of aromatic hydrocarbons. Examples included are those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogenated derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation can be performed using an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. The alkaryl sulfonate typically contains from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, per alkyl-substituted aromatic moiety. The oil-soluble sulfonate or alkaryl sulfonic acid can be neutralized with the metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrolysates, nitrates, borates and ethers. The amount of metal compound is selected in view of the desired TBN for the final product, but typically the amount is about 100-220 mass of the stoichiometrically required value. % (Preferably at least 125% by weight).

Metal salts of phenols and sulfurized phenols are prepared by reaction with suitable metal compounds such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Can do. Sulfurized phenols are obtained by reacting phenol with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalides or sulfur dihalides, and generally two or more phenols are bridged by sulfur-containing bridges. It can be produced by forming a product that is a mixture of compounds.
Carboxylate detergents such as salicylates can be prepared by reacting aromatic carboxylic acids with suitable metal compounds such as oxides or hydroxides, and neutral or overbased products are Can be obtained by methods well known in the art. The aromatic portion of the aromatic carboxylic acid can contain heteroatoms such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms, more preferably the moiety contains 6 or more carbon atoms, for example benzene is a preferred moiety. The aromatic carboxylic acid can include one or more aromatic moieties, such as one or more benzene rings, fused or linked via an alkylene bridge.
A preferred substituent in oil-soluble salicylic acid is an alkyl substituent. In alkyl-substituted salicylic acids, the alkyl group advantageously contains 5 to 100, preferably 9 to 30, especially 14 to 20 carbon atoms. When two or more alkyl groups are present, the average number of carbon atoms in the entire alkyl group is preferably at least 9 in order to ensure sufficient oil solubility.

The lubricating oil composition of the present invention preferably includes one or more metal detergents that are neutral or overbased alkali or alkaline earth metal salicylates. Highly preferred salicylate detergents include alkaline earth metal salicylates, especially magnesium and calcium, especially calcium salicylate. The metal salicylate can be the only metal-containing detergent present in the lubricating oil composition according to all aspects of the present invention. Alternatively, other metal-containing detergents such as metal sulfonates or phenates may be present in the lubricating composition. Preferably, the salicylate detergent provides the majority of the detergent additive in the lubricating oil composition.
The total amount of metal-containing detergent additive present in the lubricating oil composition according to any aspect of the present invention is in the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the active substance. Is appropriate.
Antiwear additive: This is based on compounds containing sulfur or phosphorous or both, which reduce friction and excessive wear and are usually capable of depositing polysulfide films on the surfaces involved, for example. It is. Of note is a metal salt of dihydrocarbyl dithiophosphate, where the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, copper or preferably zinc.

The metal salt of dihydrocarbyl dithiophosphoric acid, according to known techniques, first forms dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or phenols with P ₂ S ₅ and then forms the formed DDPA. It can be produced by neutralizing with a metal compound. For example, dithiophosphoric acid can be produced by reacting a mixture of primary and secondary alcohols. Alternatively, it is possible to produce dithiophosphoric acid whose hydrocarbyl group is completely secondary in character, or whose hydrocarbyl group is completely primary in character. Any basic or neutral metal compound may be used to produce the metal salt, but oxides, hydroxides and carbonates are most commonly used. Commercial additives often contain an excess of metal due to the use of an excess of the basic metal compound in the neutralization reaction.
A preferred zinc dihydrocarbyl dithiophosphate (ZDDP) is an oil-soluble salt of dihydrocarbyl dithiophosphate and can be represented by the following formula:

Where R and R ′ are the same or different hydrocarbyl groups, which groups contain 1 to 18, preferably 2 to 12 carbon atoms, and are alkyl, alkenyl, aryl, arylalkyl, alkaryl and fatty Includes groups such as cyclic groups. Particularly preferred as R and R ′ groups are alkyl groups having 2 to 8 carbon atoms. Thus, the group is for example ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil solubility, the total number of carbon atoms (ie, R and R ′) in the dithiophosphoric acid will generally be about 5 or greater. The zinc dihydrocarbyl dithiophosphate can thus comprise zinc dialkyldithiophosphate.
The ZDDP is based on the total mass of the lubricating oil composition and as measured according to ASTM D5185, the lubricating oil has at least 500 ppm by mass, such as at least 600 ppm by weight or at least 800 ppm by weight. It is added to the lubricating oil composition in an amount sufficient to provide phosphorous.
The ZDDP is suitably based on the total weight of the lubricating oil composition and measured according to ASTM D5185, with the lubricating oil having a phosphorous of 1,200 ppm by weight or less, preferably 1,000 ppm by weight or less. Is added to the lubricating oil composition in an amount sufficient to provide.

Viscosity modifier (VM): This functions to impart high and low temperature operability to the lubricating oil. The VM used may have its only function or may be multifunctional. Multifunctional viscosity modifiers that also function as dispersants are likewise known. Suitable viscosity modifiers include polyisobutylene, copolymers of ethylene and propylene and higher α-olefins, polymethacrylates, polyalkyl methacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds, copolymers of styrene and acrylates. Polymers and partially hydrogenated copolymers of styrene / isoprene, styrene / butadiene and isoprene / butadiene, and partially hydrogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene. Suitable viscosity modifiers for all aspects of the present invention include copolymers of unsaturated dicarboxylic acids and vinyl compounds, copolymers of styrene and acrylic esters, and most preferably styrene / isoprene, styrene / butadiene, and Isoprene / butadiene partially hydrogenated copolymers and partially hydrogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene. The preferred styrene / isoprene, styrene / butadiene and partially hydrogenated copolymers of isoprene / butadiene may be random copolymers, but are preferably block copolymers. The preferred styrene / isoprene, styrene / butadiene and partially hydrogenated copolymers of isoprene / butadiene and partially hydrogenated homopolymers of butadiene and isoprene and isoprene / divinylbenzene are linear polymers or star (radial) polymers. possible.
Linear block copolymers useful in the practice of the present invention can be represented by the following general formula:
A _z- (BA) _y -B _x
Where A is a polymer block containing primarily monoalkenyl aromatic hydrocarbon monomer units; B is a polymer block containing primarily conjugated diolefin monomer units; x and z are numbers independently equal to 0 or 1 And y is a whole number ranging from 1 to about 15.

Useful tapered linear block copolymers can be represented by the following general formula:
AA / BB
Where A is a polymer block containing primarily monoalkenyl aromatic hydrocarbon monomer units; B is a polymer block containing primarily conjugated diolefin monomer units; and A / B is monoalkenyl aromatic hydrocarbon and conjugated diene. It is a tapered segment containing both olefin units.
Star or radial homopolymers or random copolymers of diene (s) (eg, isoprene and / or butadiene) can generally be represented by the following general formula:
(B) _n -C
Wherein B and C are as previously defined; and n is a number ranging from 3 to 30; C is a core of a radial polymer formed using a multifunctional coupling agent; B 'Is a polymer block mainly containing conjugated diolefin units, where B' may be the same as or different from B; and n 'and n "are integers representing the number of arms of each type, and n The sum of 'and n' will be a number in the range of 3-30.
Star or radial block copolymers can generally be represented by the following general formula:
(B _x- (AB) _y -A _z ) _n -C; and
(B ' _x- (AB) _y -A _z ) _n' -C (B ') _n''
Wherein A, B, x, y and z are as previously defined; n is a number in the range of 3 to 30; C is a radial polymer formed using a multifunctional coupling agent. B 'is a polymer block mainly containing conjugated diolefin units, which B' may be the same as or different from B; and n 'and n "are integers representing the number of arms of each type And the sum of n ′ and n ″ will be a number in the range of 3-30.

As used herein in connection with the composition of a polymer block, the term “predominantly” refers to a specified monomer or monomer type that is a principal component within the polymer block. , Means present in an amount of at least 85% by weight of the block.
The lubricating oil composition according to all aspects of the present invention comprises one or more star polymer viscosity modifiers, one or more linear polymer viscosity modifiers or a mixture of linear and star polymer viscosity modifiers. Can be included.
Oil-soluble viscosity modifying polymers generally have a weight average molecular weight in the range of 10,000 to 1,000,000, preferably 20,000 to 500,000, which can be measured by gel permeation chromatography or by light scattering methods.
In one aspect of the invention, the viscosity modifier comprises a polymethacrylate, polyalkylmethacrylate or methacrylate copolymer based viscosity modifier. In a preferred embodiment, the polymethacrylate, polyalkylmethacrylate or methacrylate copolymer based viscosity modifier is the only viscosity modifier in the lubricating oil composition.

Anti-oxidants: Also often referred to as oxidation inhibitors, they increase the resistance of the above compositions to oxidation and bind peroxides and modify them to make them harmless. Can function by decomposing the peroxide, or by deactivating the oxidation catalyst. Oxidative degradation can be manifested by sludge in the lubricant, varnish-like deposits on the metal surface, and by increased viscosity.
Examples of suitable antioxidants are selected from copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine-containing antioxidants, hindered phenolic antioxidants and dithiophosphate derivatives. A preferred antioxidant is an ashless antioxidant. Preferred ashless antioxidants are ashless aromatic amine-containing antioxidants, ashless hindered phenolic antioxidants, and mixtures thereof. Preferably, one or more antioxidants are present in the lubricating oil composition according to all aspects of the present invention. In a preferred embodiment, the lubricating oil composition according to the present invention comprises a combination of an aromatic amine antioxidant and a hindered phenol antioxidant, and optionally a sulfurized olefin antioxidant.
Rust inhibitor: A rust inhibitor selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkylsulfonic acids can be used.
In a preferred embodiment according to the present invention, no copper-containing additive is present in the lubricating oil composition.

Demulsifying component: A small amount of a demulsifying component can be used. A preferred demulsifying component is described in EP 330,522. This is obtained by reacting an adduct obtained by reacting alkylene oxide and bis-epoxide with a polyhydric alcohol. The demulsifier should be used at a level not exceeding 0.1 mass% active ingredient. A treat rate of 0.001 to 0.05 mass% active ingredient is convenient.
Pour point depressant: This is otherwise known as a lube oil flow improver and lowers its minimum temperature at which the fluid will flow or can be poured. Such additives are well known. Typical of these additives that improve the low temperature fluidity of the fluid are C ₈ -C ₁₈ dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates and the like.
Antifoam: Foam control can be provided by a number of compounds including polysiloxane type antifoams such as silicone oil or polydimethylsiloxane.
Suitable additional additives and their general treatment rates are discussed below. All the values listed are stated as mass percent active ingredient in a fully formulated lubricant.

(I)：粘度調整剤は、マルチグレードオイルにおいてのみ使用される。

(I): Viscosity modifiers are used only in multigrade oils.

The final lubricating oil composition of the present invention, typically produced by blending the above additives or each of them with the base oil, is 5-25% by weight, preferably 5-18% by weight, typically Can contain 7-15% by weight of these additives, the remainder being an oil with lubricating viscosity.
As is known in the art, several additives can provide a number of effects, for example, a single additive can act as a dispersant and as an oxidation inhibitor.
The individual additives can be incorporated into the base stock in any convenient manner. Thus, each of the components can be added directly into the base oil or base oil blend by dispersing or dissolving the components at a desired concentration level within the base oil or base oil blend. Such a blending process can be performed at ambient or elevated temperatures.
Preferably, all of the additives other than the viscosity modifier and the pour point depressant are blended into a concentrate or additive package, which here produces a finished lubricant later. Is described as an additive package to be blended into the base stock. Typically, the concentrate is added to the additive (1) in an amount suitable to provide the desired concentration in the final formulation when it is combined with a predetermined amount of base lubricant. Or) will be prescribed.
Preferably, the concentrate is produced according to the method described in US 4,938,880. This patent describes the preparation of a premix consisting of an ashless dispersant and a metal detergent that is pre-blended at a temperature of at least about 100 ° C. The premix is then cooled to at least 85 ° C. and additional ingredients are added.

The final crankcase lubricating oil formulation can utilize the concentrate or additive package at 2-20% by weight, preferably 4-18% by weight and most preferably 5-17% by weight. The rest is base stock.
The lubricating oil composition according to the present invention has a sulfated ash content (ASTM D874) of 1.2% by mass or less, preferably 1.1% by mass or less, more preferably 1.0% by mass or less, based on the total mass of the composition. Can have. The lubricating oil composition of the present invention suitably has a sulfated ash content (ASTM D874) of at least 0.4 wt%, preferably at least 0.5 wt%, such as at least 0.6 wt%, based on the total weight of the composition. Have. Suitably the sulfated ash content of the lubricating oil composition is in the range of 0.4 to 1.2% by weight, preferably in the range of 0.6 to 1.0% by weight (ASTM D874).
The amount of sulfur in the lubricating oil composition will depend on the particular application of the lubricating oil composition. The lubricating oil composition may contain sulfur in an amount of up to 0.4 wt%, for example up to 0.35 wt% sulfur (ASTM D2622), based on its total weight. Generally, the lubricating oil composition will contain at least 0.1 wt%, or even at least 0.2 wt% sulfur (ASTM D2622), based on its total weight.
Suitably, the lubricating oil composition according to all aspects and embodiments of the present invention has a total base number (TBN) of 4-15 mg KOH / g, preferably 4-10 mg KOH / g, as measured according to ASTM D2896. Can have.

The invention will now be described in the following examples, which do not limit the scope of the invention.
Example 1
The Schwingung Reibung Verschleiss “SRV” supplied by Optimol is used to evaluate the friction and wear properties of liquid lubricants over a wide range of applications. The test oil forms a film between the ball and the disk, which is engaged in sliding and reciprocating strokes across the disk, and the friction between the metal-metal contacts is measured. This is used to evaluate the frictional properties of the oil's boundary regime. There are a variety of specimens and arrangements that can be used in SRV. In these examples, the average friction was recorded at a frequency of 20 Hz and a temperature of 80 ° C.
Two oils with the formulations presented in Table 1 below were tested, and their average coefficient of friction was recorded under each load shown in Table 2 below.

1：この添加剤パッケージはオイル1およびオイル2に対して同一の組成を有しており、また非ホウ酸化およびホウ酸化ポリイソブテニルサクシンイミド分散剤を含有する分散剤の組合せ；サリチル酸カルシウム洗浄剤；サリチル酸マグネシウム洗浄剤；ヒンダードフェノールとジフェニルアミン酸化防止剤との組合せ；およびジアルキルジチオリン酸亜鉛を含んでいた。
2：ダイマー型モリブデンジチオカルバメート、サクラルーベ(Sakuralube) 525。
3：トリマー型モリブデンジチオカルバメート、インフィニウムUK社(Infineum UK Ltd)から入手。
4：インフィニウムUK社(Infineum UK Ltd)から入手し得る。
5：1H-ベンゾトリアゾール-1-メタンアミン, N,N-ビス(2-エチルヘキシル)-ar-メチル、バスフ(BASF)社から入手し得る。
8：この添加剤パッケージはオイル3および4に対して同一の組成を持ち、また非ホウ酸化およびホウ酸化ポリイソブテニルサクシンイミド分散剤を含む分散剤の組合せ；サリチル酸カルシウム洗浄剤；サリチル酸マグネシウム洗浄剤；ヒンダードフェノールおよびジフェニルアミン酸化防止剤の組合せ；消泡剤；およびジアルキルジチオリン酸亜鉛を含んでいた。

1: This additive package has the same composition for Oil 1 and Oil 2 and also a combination of dispersants containing non-borated and borated polyisobutenyl succinimide dispersant; calcium salicylate wash A magnesium salicylate detergent; a combination of hindered phenol and diphenylamine antioxidant; and a zinc dialkyldithiophosphate.
2: Dimer-type molybdenum dithiocarbamate, Sakuralube 525.
3: Trimmer type molybdenum dithiocarbamate, obtained from Infineum UK Ltd.
4: Available from Infineum UK Ltd.
5: 1 H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) -ar-methyl, available from BASF Corporation.
8: This additive package has the same composition for oils 3 and 4, and a combination of dispersants including non-borated and borated polyisobutenyl succinimide dispersant; calcium salicylate detergent; magnesium salicylate detergent A hindered phenol and diphenylamine antioxidant combination; an antifoaming agent; and a zinc dialkyldithiophosphate.

From these data, it can be seen that oils 2 and 4, which contain a combination of a molybdenum compound and Irgamet 39, exhibit a significantly lower coefficient of friction than the corresponding oil which does not contain the irgamet 39.
Example 2
Four more oils with the formulations presented in Table 3 below were tested, and the average coefficient of friction was recorded under each load shown in Table 4 below.

6：この添加剤パッケージは表3における全てのオイルについて同一の組成を持ち、また非ホウ酸化およびホウ酸化ポリイソブテニルサクシンイミド分散剤を含有する分散剤の組合せ；サリチル酸カルシウム洗浄剤；サリチル酸マグネシウム洗浄剤；ヒンダードフェノールおよびジフェニルアミン酸化防止剤の組合せ；およびジアルキルジチオリン酸亜鉛を含んでいた。
2：ダイマー型モリブデンジチオカルバメート、サクラルーベ(Sakuralube) 525。
5：1H-ベンゾトリアゾール-1-メタンアミン, N,N-ビス(2-エチルヘキシル)-ar-メチル、バスフ(BASF)社から入手し得る。
7：インフィニウムUK社(Infineum UK Ltd)から入手し得る。

6: This additive package has the same composition for all oils in Table 3 and also a combination of dispersants containing non-borated and borated polyisobutenyl succinimide dispersant; calcium salicylate detergent; magnesium salicylate A detergent; a combination of hindered phenol and diphenylamine antioxidant; and a zinc dialkyldithiophosphate.
2: Dimer-type molybdenum dithiocarbamate, Sakuralube 525.
5: 1 H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) -ar-methyl, available from BASF Corporation.
7: Available from Infineum UK Ltd.

  The data in Table 4 demonstrates that the addition of an ethoxylated amine friction modifier to a lubricant containing a combination of molybdenum dithiocarbamate and a benzotriazole derivative further reduced the friction coefficient of the lubricant.

Claims (17)

A lubricating oil composition for automobile engines,
(A) Base oil with lubricating viscosity;
(B) at least one benzotriazole derivative represented by the following formula (I):

Formula (I)
Here, R ⁵ is a hydrocarbyl group having 1 to 3 carbon atoms,
R ⁶ is a tertiary amino group represented by the following formula:

Where R ⁷ and R ⁸ are independently hydrocarbyl groups having from 3 to 10 carbon atoms;
(C) At least one molybdenum dithiocarbamate compound represented by either the following formula (II) or the following formula (III):

Formula (II)
Here, R _{1 to} R ₄ independently represent a linear, branched or aromatic hydrocarbyl group having 1 to 24 carbon atoms, and X _{1 to} X ₄ independently represent an oxygen atom or a sulfur atom. Means
Mo ₃ S _k L _n Q _z formula (III)
L is an independently selected ligand comprising an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is 1-4, k Is selected from the group consisting of neutral, electron donating compounds such as water, amines, alcohols, phosphines and ethers, z is in the range of 0-5, and non-stoichiometric. Including typical values;
(D) One or more additional additives selected from metal-containing or ashless detergents, ashless antioxidants, antiwear additives, corrosion inhibitors, rust inhibitors, viscosity index improvers and dispersants ,
Including
The lubricating oil composition contains 100 to 2,000 ppm of molybdenum derived from component (C) in total, and the benzotriazole derivative (B) is in an amount of 0.001 to 5 mass% in the lubricating oil. The lubricating oil composition present in The lubricating oil composition for automobile engines according to claim 1, wherein the benzotriazole derivative (B) has the following structure:

  The benzotriazole derivative (B) is present in an amount of 0.001 to 5% by weight, preferably 0.01 to 2% by weight, for example 0.01 to 1% by weight, based on the active substance. Item 3. A lubricating oil composition for automobile engines according to Item 1 or 2.   The lubricating composition for automobile engines according to claim 3, wherein the benzotriazole derivative is present in the lubricating oil composition according to the present invention in an amount of 0.01 to 0.04% by mass based on the active substance. .   The lubricating oil composition for automobile engines according to any one of claims 1 to 4, wherein the molybdenum dithiocarbamate compound (C) contains only a dimer-type molybdenum dithiocarbamate having the formula (II).   The molybdenum dithiocarbamate compound (C) comprises a mixture of dimeric molybdenum dithiocarbamate having the formula (II) and trimer molybdenum dithiocarbamate having the formula (III). The lubricating oil composition for automobile engines as described.   The lubricating oil composition for automobile engines according to any one of claims 1 to 6, wherein the lubricating oil composition contains 450 to 2,000 ppm of molybdenum derived from the molybdenum dithiocarbamate component (C) in a total amount.   The lubricating oil composition for automobile engines according to claim 7, wherein the molybdenum dithiocarbamate compound (C) provides 600 to 900 ppm of molybdenum to the lubricating oil composition. The lubricating oil composition for automobile engines according to any one of claims 1 to 8, further comprising an amine friction modifier having a structure according to the following formula (IV):

Formula (IV)   The amount of the amine friction modifier having the formula (IV) in the lubricating oil composition does not exceed 5% by weight, preferably does not exceed 2% by weight, based on the total weight of the lubricating oil composition, more The lubricating oil composition for automobile engines according to claim 9, preferably not exceeding 0.5% by mass.   One or more metal detergents wherein the lubricating oil composition is a neutral or overbased alkali or alkaline earth metal salicylate, preferably a neutral or overbased magnesium and / or calcium detergent The lubricating oil composition for automobile engines according to any one of claims 1 to 10, further comprising:   The automotive engine lubrication according to any one of the preceding claims, wherein the lubricating oil composition further comprises one or more oil-soluble zinc dihydrocarbyl dithiophosphates, preferably containing only secondary alkyl groups. Oil composition.   A method of lubricating an automobile engine, comprising the step of lubricating the engine with a lubricating oil composition for an automobile engine according to any one of claims 1-12.   Lubricating oil as defined in any one of claims 1 to 12, comprising a base oil (A) having a lubricating viscosity and at least one molybdenum dithiocarbamate compound (C) in connection with the lubrication of automobile engines. Claims 1-12 as an effective minor additive to improve the friction reducing performance characteristics of the molybdenum dithiocarbamate compound (s) (C) during operation of the automobile engine in a composition. The use of at least one benzotriazole derivative (B) as defined in any one of the above, wherein the molybdenum dithiocarbamate compound (s) (C) is added to the lubricating oil composition at 100-2. Said use giving 1,000 ppm of molybdenum.   In relation to automotive engine lubrication, at least one benzotriazole derivative (B) as defined in any one of claims 1 to 12 and at least one of any of claims 1 to 12. The automotive engine as an effective minor additive combination in a lubricating oil composition containing a base oil (A) having a lubricating viscosity in combination with a molybdenum dithiocarbamate compound (C) as defined in paragraph 1 The molybdenum oil composition is used for improving the friction reducing properties of the lubricating oil composition during operation of the molybdenum dithiocarbamate compound (s) (C) in a range of 100 to 2,000 ppm. The use given to things.   In relation to automotive engine lubrication, at least one benzotriazole derivative (B) as defined in any one of claims 1 to 12 and at least one of any of claims 1 to 12. The automotive engine as an effective minor additive combination in a lubricating oil composition containing a base oil (A) having a lubricating viscosity in combination with a molybdenum dithiocarbamate compound (C) as defined in paragraph 1 Wherein the molybdenum dithiocarbamate compound (s) (C) provides the lubricating oil composition with 100 to 2,000 ppm of molybdenum. use.   Use according to any one of claims 14 to 16, wherein the automobile engine operates at a temperature of 80C or less.