JP2001262173A - Lubricating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricating composition capable of maintaining a friction reduction action (long drain effect) even in a long-term use. SOLUTION: This lubricating composition comprises a lubricating base, an organomolybdenum compound as a component (A) (a compound corresponding to a component (B) is omitted) and a reaction product between a fatty acid or naphthenic acid and molybdenum or zinc or their oxide as the component (B). The organomolybdenum compound of the component (A) is preferably represented by general formula (1), general formula (2) or general formula, R9-NH-R10 (3) (R1 to R8 are each a hydrocarbon group; R9 and R10 are each a hydrogen atom or a hydrocarbon group; and X1 to X8 are each sulfur or oxygen).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lubricating composition.

[0002]

2. Description of the Related Art At present, the situation surrounding automobiles is becoming stricter, such as fuel efficiency regulations and exhaust gas regulations. Behind this are environmental issues such as global warming, air pollution and acid rain, and resource protection from concerns over the limited depletion of petroleum energy. As a countermeasure, improving fuel efficiency is currently the most effective. In order to save fuel consumed by automobiles, that is, to promote so-called fuel saving, the weight of the automobile itself, the improvement of the engine, etc., as well as the improvement of the automobile itself, as well as the reduction of the viscosity of engine oil to prevent friction loss in the engine, Improvement of engine oil, such as addition of a good friction modifier, is also an important factor. The engine oil acts as a lubricant between the piston and the liner, but since there is much fluid lubrication in this part, friction loss can be reduced by reducing the viscosity of the engine oil. For this reason, in recent years, the viscosity of engine oil has been reduced, but problems such as deterioration of sealability and increase in wear due to the reduction in viscosity have newly occurred.
Engine oil also plays an important role in lubrication of valve trains, bearings, etc., but in this area, mixed lubrication and boundary lubrication are common, so reducing the viscosity of engine oil causes increased wear. ing. Therefore, a friction modifier, an extreme pressure agent, and the like are added for the purpose of reducing friction loss due to lowering the viscosity of engine oil and preventing wear.

[0003] Organic molybdenum compounds have an excellent friction reducing effect and are therefore added to various lubricating oils, but they are particularly effective in reducing fuel consumption in engine oils and are indispensable for fuel saving oils. Is becoming an additive. Even if the fuel-saving oil exhibits excellent fuel-saving performance at the new oil stage, it cannot be said to be an excellent fuel-saving oil unless the performance can be maintained for a long time. Therefore, it is an important theme required for the current fuel-saving oil to determine whether the friction reducing effect can be maintained even after long-term use (so-called long drain effect).

[0004]

As means for preventing deterioration of the lubricating oil, several means can be considered. As an effective means, there is a means for adding an antioxidant. As the antioxidant, a so-called primary antioxidant such as a phenolic antioxidant (for example, JP-B-6-62988) or an amine-based antioxidant (for example, JP-A-6-313183) is added. Means, so-called secondary antioxidants such as zinc dithiophosphate (for example, see JP-A-54-113).
No. 604) is well known. The present inventors have conducted intensive studies and found that when a specific reaction product was added to a lubricating oil instead of these known antioxidants, deterioration of the lubricating oil was reduced, particularly to a lubricating oil to which an organic molybdenum compound was added. On the other hand, they have found that they have the effect of suppressing the decrease of the organic molybdenum compound due to the deterioration and can improve the long drain property of the lubricating oil, and have completed the present invention.

[0005]

That is, the present invention provides an organic molybdenum compound as a component (A) on a lubricating base material (however, a compound corresponding to the component (B) is excluded);
(B) A lubricating composition containing, as a component, a reaction product of a fatty acid or naphthenic acid with molybdenum or zinc or an oxide thereof.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The component (A) of the present invention is an organic molybdenum compound. However, this organic molybdenum compound does not include the reaction product of the fatty acid or naphthenic acid as the component (B) with molybdenum or molybdenum oxide. As the organic molybdenum compound of the component (A),
For example, oxymolybdenum sulfide xanthate, a reaction product of molybdenum trioxide and an acid phosphate, a reaction product of molybdenum trioxide and a fatty acid diethanolamide, a reaction product of molybdenum trioxide and a glycerin monofatty acid ester,
Examples include succinimide, carboxylic acid amide, Mannich base, or a reaction product between a boride thereof and molybdenum trioxide. The most preferred organic molybdenum compound is oxymolybdenum sulfide dithiocarbamate (MoDTC) represented by the following general formula (1);
Or a molybdenum amine reactant (MoAm) which is a reactant of an amine represented by the general formula (3) and a compound having a pentavalent or hexavalent molybdenum atom.

[0007]

Embedded image

(Wherein R ^{1 to} R ⁴ represent a hydrocarbon group;
X ^{1 to} X ⁴ represent a sulfur atom or an oxygen atom. )

[0009]

Embedded image

(Wherein, R ^{5 to} R ⁸ represent a hydrocarbon group;
X ^{5 to} X ⁸ represent a sulfur atom or an oxygen atom. )

R ⁹ -NH-R ¹⁰ (3) (In the formula, R ⁹ and R ¹⁰ represent a hydrogen atom or a hydrocarbon group, but they are not hydrogen atoms at the same time.)

In the general formulas (1) to (3), R ^{1 to} R
Reference numeral ¹⁰ denotes a hydrocarbon group, for example, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group and the like.

The alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, Decyl, secondary decyl, undecyl,
Secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl,
Secondary tetradecyl, hexadecyl, secondary hexadecyl,
Stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl,
2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl Branched-isostearyl and the like.

Examples of the alkenyl group include vinyl,
Allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like. Examples of the aryl group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, Nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, β-naphthyl and the like can be mentioned.

Examples of the cycloalkyl group and cycloalkenyl group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclohexenyl Heptenyl and the like.

R ^{1 to} R ¹⁰ may be the same or different. That is, R ^{1 to} R ⁴ , R ^{5 to} R ⁸ , and R ^{9 to} R ¹⁰ may be the same or different. When R ^{1 to} R ⁴ are different from each other, it is preferable for achieving a long drainage (long life) of the lubricating oil composition. Among these, R ¹ ~
R ¹⁰ is preferably an alkyl group, an alkenyl group or an aryl group. More specifically, R ¹ to R ¹ of the general formula (1)
R ⁴ , that is, an alkyl group having 8 to 13 carbon atoms in sulfided oxymolybdenum dithiocarbamate,
R ^{5 to} R ⁸ , ie, an alkyl group having 6 to 13 carbon atoms in sulfurized oxymolybdenum dithiophosphate, and R ^{9 to} R ¹⁰ in general formula (3), ie, 6 carbon atoms in a molybdenum amine reactant. ~ 18 alkyl groups are preferred. This is because if the group represented by R ^{1 to} R ¹⁰ has too small a carbon number, the oil solubility becomes poor, and if the carbon number is too large, the melting point becomes high, handling becomes poor, and activity becomes low. .

In the general formulas (1) and (2),
X ¹ to X ^4, X ⁵ to X ⁸ are each a sulfur atom or an oxygen atom may be all a sulfur atom or an oxygen atom of ^{X 1 ~X 4, X 5 ~X} 8, 4 one of X ¹ X ⁴ or X ^{5 to} X ⁸ may each be a sulfur atom or an oxygen atom. However, considering lubricity and corrosiveness, the abundance ratio of sulfur atoms / oxygen atoms is 1/3 to Particularly preferred is 3/1.

The pentavalent or hexavalent molybdenum compound to be reacted with the amine represented by the general formula (3) is, for example, molybdenum trioxide or a hydrate thereof (MoO ₃ .n).
H ₂ O), molybdic acid (H ₂ MoO ₄ ), alkali metal molybdate (M ₂ MoO ₄ ; M is an alkali metal atom), ammonium molybdate ｛(NH ₄ ) ₂ MoO ₄
Or (NH ₄ ) ₆ [Mo ₇ O ₂₄ ] · 4H ₂ O}, MoC
_{l 5, MoOCl 4, MoO 2} Cl 2, MoO 2 Br 2, Mo
_{Although 2} O ₃ Cl _{6 and the} like can be mentioned, hexavalent molybdenum compounds are preferable in consideration of the yield of the molybdenum amine compound. Among the hexavalent molybdenum compounds, readily available molybdenum trioxide or hydrates thereof, molybdic acid, alkali metal molybdate, ammonium molybdate and the like are preferable.

As the component (A), oxymolybdenum dithiocarbamate sulfide (Mo) represented by the general formula (1) is used.
DTC), a sulfurized oxymolybdenum dithiophosphate (MoDTP) represented by the general formula (2), or a molybdenum amine reaction which is a reaction product of an amine represented by the general formula (3) and a compound having a pentavalent or hexavalent molybdenum atom. Although only one kind of the compound (MoAm) may be used or two or more kinds may be used in combination, it is preferable to use at least one kind of oxymolybdenum dithiocarbamate (MoDTC) represented by the general formula (1).

The addition amount of component (A) is not particularly limited, but if the addition amount is too small, the effect of reducing friction is not sufficient, and if the addition amount is too large, sludge and corrosion tend to be caused. When the amount of the organic molybdenum compound is relatively small (generally, about 300 ppm by mass or less in terms of molybdenum with respect to the lubricating base material), the abrasion resistance effect is obtained.
It is said that when the amount is relatively large, the effect of reducing friction is remarkably exhibited. Therefore, the addition amount is preferably 10 to 30,000 mass ppm, more preferably 50 to 20,000 mass pp, based on the amount of molybdenum relative to the lubricating base material.
m, more preferably 100 to 10,000 ppm by mass.

The component (B) of the present invention is a reaction product of a fatty acid or naphthenic acid and a salt of molybdenum or zinc or an oxide of molybdenum or zinc. Fatty acids include, for example, butanoic acid, hexanoic acid, octanoic acid, 2-
Ethylhexanoic acid, nonanoic acid, decanoic acid, lauric acid,
Examples include fatty acids such as tridecanoic acid, isotridecanoic acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid, linolenic acid, and naphthenic acid. The fatty acid preferably has about 6 to 18 carbon atoms. If the number of carbon atoms is too large, the melting point of the fatty acid increases, and it becomes difficult to efficiently react with molybdenum or the like.

The method for producing a reaction product of a fatty acid or naphthenic acid with molybdenum or zinc or an oxide thereof is not particularly limited. Usually, however, a mixture of a fatty acid or naphthenic acid with molybdenum or zinc or an oxide thereof is used. Then, the reaction may be performed by heating at a temperature of about 100 to 200 ° C. When using zinc or molybdenum oxide,
During the reaction, water may be generated in some cases, but this may be removed by distillation under reduced pressure if necessary.

The component (B) of the present invention not only improves lubricity, but also suppresses and prevents deterioration of the lubricating base material and the organic molybdenum compound as the component (A) due to long-term use. is there. Thereby, even when the lubricating composition is deteriorated, a decrease due to decomposition of the component (A) can be minimized, and as a result, a so-called excellent long drain effect can be exhibited. The amount of the component (B) added is preferably 5 to 20,000 mass ppm, more preferably 15 to 10,000 mass ppm, and still more preferably 20 to 5 mass ppm of molybdenum or zinc with respect to the lubricating base material. 2,000 mass ppm.

The component (C) of the present invention has the following general formula (4)
Is a zinc dithiophosphate (ZDTP).

[0025]

Embedded image

(Wherein R ¹¹ and R ¹² represent a hydrocarbon group, a
Represents a number from 0 to 1/3. ) By adding the component (C) to the lubricating composition of the present invention, the antioxidant property and the long drain property are further improved. In the general formula (4),
R ¹¹ and R ¹² are hydrocarbon groups. As R ¹¹ and R ¹² , an alkyl group, an alkenyl group, an aryl group and the like are preferable. Among these, an alkyl group having 3 to 14 carbon atoms is preferable. Further, as the component (C), two or more kinds of zinc dithiophosphates having different R ¹¹ and R ¹² may be used in combination. a is 0 to 1/3, when a = 0, it is called neutral zinc dithiophosphate, and when a = 1/3,
It is called basic zinc dithiophosphate. The addition amount of the component (C) is not particularly limited, but it is preferable to add a certain amount in order to exhibit a practical friction reducing effect and an antioxidant effect. In some cases, the amount of phosphorus is preferably 10 to 30,000 with respect to the lubricating base material.
Mass ppm, more preferably 50 to 20,000 mass p
pm, more preferably 100 to 10,000 mass ppm
It is.

The lubricating composition of the present invention may contain (D1) a metal detergent as a component (D) depending on the purpose of use.
(D2) an ashless dispersant, (D3) a compound containing a phosphorus atom, (D4) a compound containing a phosphorus atom and a sulfur atom,
(D5) a compound containing a sulfur atom but not containing a metal atom, (D6) an antioxidant, (D7) an organometallic compound (however, excluding those falling under the component (B)), and (D8) a metal atom An oiliness improver containing no phosphorus atom and sulfur atom, (D9) a rust preventive, (D10) a viscosity index improver, (D9)
11) metal deactivator, (D12) defoamer, (D13)
Solid lubricants and the like can be added.

As the metal detergent as the component (D1),
For example, metal sulfonate, metal phenate, metal salicylate, metal phosphonate and the like can be mentioned. Examples of the metal sulfonate include (mono or di) alkyl benzene sulfonic acid metal salt, (mono or di) alkyl naphthalene sulfonic acid metal salt, and petroleum sulfonic acid metal salt. Examples of the metal phenate include (mono or di) alkylphenol metal salts, thiobis {(mono or di) alkylphenol} metal salts, and methylene bis {(mono or di) alkylphenol} metal salts. Examples of the metal salicylate include (mono or di) alkyl salicylic acid metal salt, thiobis {(mono or di) alkyl salicylic acid} metal salt, and methylene bis {(mono or di) alkyl salicylic acid} metal salt. As the metal atom, an alkali metal or an alkaline earth metal is preferable, and calcium, magnesium, and barium are more preferable.

The above compounds are generally called neutral salts. A basic or overbased metal detergent which has been basified with a metal oxide or metal hydroxide while blowing carbon dioxide into these neutral salts is preferably used. The overbased product is usually contained in the form of a carbonate. The total base number (TBN) of these basic or overbased metal detergents is generally between 100 and 500 mg KOH / g.
It is about.

Most preferred among these metal detergents are neutral, basic or overbased calcium salicylates or calcium sulfonates. (D
The preferable amount of the component (1) is 0.1 to the lubricating base material.
It is about 5 to 10% by mass. Examples of the ashless dispersant as the component (D2) include succinimide, benzylamine, succinate, and boron-modified products thereof. As the succinimide, for example, a compound represented by the following formula (D2-1) (excluding arrows)

[0031]

Embedded image

(R represents a polyalkenyl group such as a polybutenyl group, and n represents a number of about 1 to 10) or a compound represented by the following formula (D2-2) (excluding arrows)

[0033]

Embedded image

(R represents a polyalkenyl group such as a polybutenyl group, and n represents a number of about 1 to 10.). These general formulas (D2-2) and (D2-2)
The molecular weight of the polyalkenyl group is usually 300 to 4,000
It is about 0. N is preferably 2 to 5. As benzylamine (Mannich reaction product), for example, a compound represented by the following general formula (D2-3) (however, excluding arrows)

[0035]

Embedded image

(R represents a polyalkenyl group such as a polybutenyl group, and n represents a number of about 1 to 10.). The molecular weight of the polyalkenyl group is usually 300 to
It is about 4,000. N is preferably 2 to 5. Examples of the succinic acid ester include compounds represented by the following general formula (D2-4) (however, except for arrows)

[0037]

Embedded image

(R represents a polyalkenyl group such as a polybutenyl group, and R ′ represents a residue obtained by removing one hydroxyl group from a monool or a polyol.) Or a compound represented by the following formula (D2-5) (However, except for arrows)

[0039]

Embedded image

(R represents a polyalkenyl group such as a polybutenyl group, and R ′ represents a residue obtained by removing two hydroxyl groups from a polyol.). The molecular weight of the polyalkenyl groups of these general formulas (D2-4) and (D2-5) is usually about 300 to 4,000. Examples of the boron-modified product of the above compound include, for example, the following substituent (D2-a) at the arrow of the above general formula.

[0041]

Embedded image

Or the following general formula (D2-b)

[0043]

Embedded image

And the like are coordinated. The nitrogen content in the ashless dispersant is usually 0.5 to 2.0% by mass.
It is about. Among these ashless dispersants, preferred is succinimide or a boron-modified product thereof. (D
2) The preferred blending amount of the component is 0.1% based on the lubricating substrate.
It is about 5 to 10% by mass.

Examples of the compound containing a phosphorus atom as the component (D3) include organic phosphorus compounds such as phosphine, phosphine oxide, phosphinite, phosphite, phosphinate, phosphite, phosphonate, phosphate, and phosphoramidate. .
These compounds mainly improve lubricity and wear resistance, but may also act as antioxidants.

Examples of the organic phosphine represented by (R) ₃ P include, for example, tributylphosphine, trihexylphosphine, trioctylphosphine, tri (2-ethylhexyl) phosphine, trinonylphosphine, tridecylphosphine, trilaurylphosphine, and trilaurylphosphine. Examples include myristyl phosphine, tripalmityl phosphine, tristearyl phosphine, trioleyl phosphine, triphenyl phosphine, tricresyl phosphine, and the like. (R) The ₂ P- (CH ₂₎ alkylidene bis phosphine represented by _n -P (R) _2, for example, methylenebis (dibutylphosphine), methylenebis (dihexylphosphine), methylenebis (dioctyl phosphine)
Methylenebis (di-2-ethylhexylphosphine), methylenebis (dinonylphosphine), methylenebis (didecylphosphine), methylenebis (dilaurylphosphine), methylenebis (dimylstyrylphosphine), methylenebis (dipalmitylphosphine), methylenebis (distearylphosphine) ), Methylenebis (dioleylphosphine), methylenebis (diphenylphosphine), methylenebis (dicresylphosphine) and the like.

Examples of the organic phosphine oxide represented by (R) ₃ P ＝ O include, for example, tributyl phosphine oxide, trihexyl phosphine oxide, trioctyl phosphine oxide, tri (2-ethylhexyl) phosphine oxide, trinonyl phosphine oxide, and trinonyl phosphine oxide. Examples include decyl phosphine oxide, trilauryl phosphine oxide, trimyristyl phosphine oxide, tripalmityl phosphine oxide, tristearyl phosphine oxide, trioleyl phosphine oxide, triphenyl phosphine oxide, and tricresyl phosphine oxide.

As the organic phosphite represented by (RO) ₃ P, for example, monobutyl phosphite, dibutyl phosphite, tributyl phosphite (hereinafter collectively referred to as “mono / di / tributyl phosphite”) Abbreviations), mono / di / trihexyl phosphite, mono / di / trioctyl phosphite, mono / di /
Tri (2-ethylhexyl) phosphite, mono / di /
Trinonyl phosphite, mono / di / tridecyl phosphite, mono / di / trilauryl phosphite, mono /
Di / trimyristyl phosphite, mono / di / tripalmityl phosphite, mono / di / tristearyl phosphite, mono / di / trioleyl phosphite, mono /
Di / triphenyl phosphite, mono / di / tricresyl phosphite and the like. Examples of other phosphites include pentaerythritol diphosphite, pentaerythritol tetraphosphite, and alkylidenebisphosphite.

The organic phosphate represented by (RO) ₃ P ＰO includes, for example, monobutyl phosphate, dibutyl phosphate, tributyl phosphate (hereinafter collectively referred to as “mono / di / tributyl phosphate”).
Abbreviated as ), Mono / di / trihexyl phosphate, mono / di / trioctyl phosphate, mono /
Di / tri (2-ethylhexyl) phosphate, mono /
Di / trinonyl phosphate, mono / di / tridecyl phosphate, mono / di / trilauryl phosphate, mono / di / trimyristyl phosphate, mono / di / tripalmityl phosphate, mono / di / tristearyl phosphate, mono / di / Trioleyl phosphate, mono / di / triphenyl phosphate, mono / di / tricresyl phosphate and the like. Further, a phosphate having a polyoxyalkylene group, for example, a phosphate of lauryl alcohol ethylene oxide and / or propylene oxide adduct and the like are also included.

Of these phosphates, mono- or diphosphates are called acidic phosphate esters and may be used after neutralization with a base such as an alkali or an amine. Examples of the alkali include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. As the amine, for example, ammonia; methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tridecylamine, cetylamine, Alkylamines such as coconut alkylamine, alkylamine derived from soybean oil, alkylamine derived from tallow, oleylamine, and stearylamine; monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, N-methyldiethanolamine; N-ethyldiethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2
-Amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ', N'-tetrakis (hydroxyethyl) ethylenediamine, N,
Alkanolamines such as N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or alkylene oxide adducts thereof; N-butyldiethanolamine, N-hexyldiethanolamine, N-
Octyldiethanolamine, N-decyldiethanolamine, N-cocoalkyldiethanolamine, alkyldiethanolamine derived from N-soy oil, alkyldiethanolamine derived from N-tallow, N-oleyldiethanolamine, N-stearyldiethanolamine, N, N-
Dibutyl monoethanolamine, N, N-dihexyl monoethanolamine, N, N-dioctyl monoethanolamine, N, N-didecyl monoethanolamine,
N, N-bis (cocoalkyl) monoethanolamine,
N, N-bis (alkyl derived from soybean oil) monoethanolamine, N, N-bis (alkyl derived from tallow) monoethanolamine, N-dioleyl monoethanolamine, N-
Examples thereof include N-long-chain alkylalkanolamines such as distearyl monoethanolamine, and alkylene oxide adducts thereof. Examples of the phosphoramidate include those obtained by subjecting the above-mentioned phosphate and the above-mentioned amine to a condensation reaction. The preferable blending amount of the component (D3) is about 0.1 to 5% by mass based on the lubricating base material.

Examples of the compound containing a phosphorus atom and a sulfur atom as the component (D4) include trithiophosphite and thiophosphate. These compounds mainly improve lubricity and wear resistance, but may also act as antioxidants.

Examples of the organic trithiophosphite represented by (RS) ₃ P include, for example, monobutyl trithiophosphite, dibutyl trithiophosphite, and tributyl trithiophosphite (hereinafter collectively referred to as “mono / di / tributylthiophosphite”). Mono / di / trihexyltrithiophosphite, mono / di / trioctyltrithiophosphite, mono / di / tri (2-ethylhexyl) trithiophosphite, mono / di / trinonyl. Trithiophosphite, mono / di / tridecyltrithiophosphite, mono / di /
Trilauryl trithiophosphite, mono / di / trimyristyl trithiophosphite, mono / di / tripalmityl trithiophosphite, mono / di / tristearyl trithiophosphite, mono / di / trioleyl trithiophosphite, mono / di / Triphenyltrithiophosphite, mono / di / tricresyltrithiophosphite and the like.

Examples of the organic thiophosphate represented by (RO) ₃ P = S include, for example, monobutyl thiophosphate, dibutyl thiophosphate and trihexyl thiophosphate (hereinafter collectively referred to as “mono / di / tributyl thiophosphate”). Abbreviated as.), Thing /
Di / trioctyl thiophosphate, mono / di / tri (2-ethylhexyl) thiophosphate, mono / di /
Trinonyl thiophosphate, mono / di / tridecyl thiophosphate, mono / di / trilauryl thiophosphate, mono / di / trimyristyl thiophosphate, mono / di / tripalmityl thiophosphate, mono / di /
Tristearyl thiophosphate, mono / di / trioleyl thiophosphate, mono / di / triphenyl thiophosphate, mono / di / tricresyl thiophosphate and the like can be mentioned. Further, dithiophosphoric acid dimers can also be used. The preferred amount of the component (D4) is about 0.1 to 5% by mass based on the lubricating base material.

Examples of the compound containing a sulfur atom as a component (D5) and containing no metal atom include lard sulfide, sulfide fish oil, sulfide whale oil, sulfide soybean oil, sulfide pinene oil,
Sulfurized coconut oil, other than sulfurized fatty acid-derived compounds such as sulfurized fatty acids, other than sulfurized single bonds, organic mono- or polysulfides, polyolefin sulfides such as isobutylene, 1,3,4-thiadiazole derivatives, thiuram disulfide, And dithiocarbamic acid esters.

The organic mono- or polysulfide is represented by the following general formula (D5-1) R-S _x -R (D5-1) (wherein R represents a hydrocarbon group, and x represents a number of about 1 to about 10). Is a compound represented by the formula:
Dimethyl monosulfide, dimethyl disulfide,
Dimethyl polysulfide (hereinafter, these are collectively abbreviated as “dimethyl mono / di / polysulfide”), diethyl mono / di / polysulfide, dipropyl mono / di / polysulfide, diisopropyl mono / di / polysulfide, dibutyl mono / di / polysulfide. , Diisobutyl mono / di / polysulfide, ditertiary butyl mono / di / polysulfide,
Dipentyl mono / di / polysulfide, diisopentyl mono / di / polysulfide, dineopentyl mono /
Di / polysulfide, ditertiary pentyl mono / di / polysulfide, dihexyl mono / di / polysulfide, diheptyl mono / di / polysulfide, dioctyl mono / di / polysulfide, di-2-ethylhexyl mono / di / polysulfide, dinonyl mono / di /
Polysulfide, ditercharinonyl mono / di / polysulfide, didecyl mono / di / polysulfide,
Diundecyl mono / di / polysulfide, didodecyl mono / di / polysulfide, ditridecyl mono / di /
Polysulfide, diisotridecyl mono / di / polysulfide, ditetradecyl mono / di / polysulfide, dihexadecyl mono / di / polysulfide, distearyl mono / di / polysulfide, diisostearyl mono / di / polysulfide, dioleyl mono / di /
Polysulfide, diicosyl mono / di / polysulfide, didocosyl mono / di / polysulfide, ditetracosyl mono / di / polysulfide, ditriacontyl mono / di / polysulfide, diphenyl mono / di /
Polysulfide, ditolyl mono / di / polysulfide, dixylyl mono / di / polysulfide, dicumenyl mono / di / polysulfide, dimesityl mono / di / polysulfide, dibenzyl mono / di / polysulfide, diphenethyl mono / di / polysulfide, distyryl mono / di / polysulfide, dicinamyl monosulfide Polysulfide, dibenzhydryl mono / di / polysulfide, ditrityl mono / di / polysulfide, di (ethylphenyl) mono / di / polysulfide, di (propylphenyl) mono / di / polysulfide, di (butylphenyl) mono / di / polysulfide, Di (pentylphenyl) mono / di / polysulfide, di (hexylphenyl) mono / di / polysulfide, di (heptyl) Phenyl) mono / di / polysulfide, di (octylphenyl) mono / di / polysulfide, di (nonylphenyl) mono / di / polysulfide, di (decylphenyl) mono / di / polysulfide, di (undecylphenyl) mono / di / Polysulfide, di (dodecylphenyl) mono / di / polysulfide, di (phenylphenyl) mono / di / polysulfide, di (benzylphenyl) mono / di / polysulfide, di (styrenated phenyl) mono / di / polysulfide, di ( (p-cumylphenyl) mono / di / polysulfide, dicyclopentyl mono / di / polysulfide, dicyclohexyl mono / di / polysulfide, dicycloheptyl mono / di / polysulfide, di (methylcyclopentyl) mono / di / polysulfide Di (methylcyclohexyl) mono / di / polysulfide, di (methylcycloheptyl) mono / di / polysulfide, etc .; di (hydrocarbyl sulfide); di (ethylhydroxyphenyl) mono / di / polysulfide, di (propylhydroxyphenyl) mono / Di / polysulfide, di (butylhydroxyphenyl) mono / di / polysulfide, di (pentylhydroxyphenyl) mono / di / polysulfide, di (hexylhydroxyphenyl) mono / di / polysulfide, di (heptylhydroxyphenyl) mono / di / Polysulfide, di (octylhydroxyphenyl) mono / di / polysulfide, di (nonylhydroxyphenyl) mono / di / polysulfide, di (decylhydroxyphenyl) mono / di / poly And dihydrocarbylphenol sulfides such as sulfide, di (undecylhydroxyphenyl) mono / di / polysulfide, and di (dodecylhydroxyphenyl) mono / di / polysulfide.

The 1,3,4-thiadiazole derivative has the following general formula (D5-2)

[0057]

Embedded image

(Wherein, R represents a hydrocarbon group or a hydrocarbon group containing a sulfur atom).

Examples of the sulfur-containing hydrocarbon group include 5-thianonyl, 2,5-dithianonyl, 3,4-
Dithiahexyl, 4,5-dithiahexyl, 3,4,5
-Trithiaheptyl, 3,4,5,6-tetrathiaoctyl, 5-thia-2-heptenyl, 4-thiacyclohexyl, 1,4-dithianaphthyl, 5- (methylthio) octyl, 4- (ethylthio) -2 -Pentenyl, 4-
(Methylthio) cyclohexyl, 4-mercaptophenyl, 4- (methylthio) phenyl, 4- (hexylthio) benzyl, stearyldithio, lauryldithio, octyldithio, stearylthio, laurylthio, octylthio, N, N-dialkyldithiocarbamoyl and the like. Among them, a group in which 2 to 4 sulfur atoms are continuously bonded is particularly preferable. Thiuram disulfide has the following general formula (D5-3)

[0060]

Embedded image

(R represents a hydrocarbon group, and R ′ represents a sulfur atom, a divalent hydrocarbon group or a divalent hydrocarbon group containing a sulfur atom.) As R ′, for example, a group represented by -S (-S) _n- (where n is 0 or a number of 1 or more), a methylene group, -S (-S) _n (-C
And a group represented by H ₂ ) _n -S (-S) _n- (where n is the same or different and is 0 or 1 or more). R is preferably a chain hydrocarbon group having 4 or more carbon atoms. Dithiocarbamic acid ester is represented by the following general formula (D5-4)

[0062]

Embedded image

(R represents a hydrocarbon group, R ′ represents a hydrogen atom, a hydrocarbon group or a group represented by COOR ″, and R ″ represents a hydrocarbon group.) (D
5) The preferable blending amount of the component is 0.1 to the lubricating base material.
It is about 1 to 10% by mass.

As the antioxidant as the component (D6),
For example, phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants and the like can be mentioned. Examples of the phenolic antioxidant include 2,6-di-tert.-
Butylphenol (hereinafter, tert.-butyl is referred to as “t-
Butyl ". ), 2,6-di-t-butyl-p
-Cresol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol,
4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4'-bis (2-methyl-6-t -Butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,
4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis (2,6
-Di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol),
2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2'-hydroxy-3'-t- Butyl-5'-methylbenzyl) -4-methylphenol, 3-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole,
Stearyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, 3- (4-hydroxy-
Oleyl 3,5-di-t-butylphenyl) propionate, dodecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5-di- tert-butylphenyl) decyl propionate, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis-3- (4
-Hydroxy-3,5-di-t-butylphenyl) propionyloxymethyldimethane, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy −3,5-
Ester of di-t-butylphenyl) propionic acid with glycerin monooleyl ether, butylene glycol 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-
3,5-di-t-butylphenyl) propionic acid thiodiglycol ester, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t -Butylphenol), 2,2 ′
-Thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-α-dimethylamino-
p-cresol, 2,6-di-tert-butyl-4- (N,
N'-dimethylaminomethylphenol), bis (3
5-di-tert-butyl-4-hydroxybenzyl) sulfide, tris {(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-tert-) Butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, bis {2-methyl-4- (3-
n-alkylthiopropionyloxy) -5-t-butylphenyl disulfide, 1,3,5-tris (4-
t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6
-Dimethyl-4-t-butyl-3-hydroxybenzyl sulfide), 6- (4-hydroxy-3,5-di-)
t-butylanilino) -2,4-bis (octylthio)
-1,3,5-triazine, 2,2-thio- {diethyl-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl)} propionate, N, N′-hexamethylenebis ( 3,5-di-t-butyl-4-hydroxy-
Hydrocinamide), 3,5-di-t-butyl-4-hydroxy-benzyl-phosphate diester, bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 3,9-bis [1, 1-dimethyl-2-Δβ-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10
-Tetraoxaspiro [5,5] undecane, 1,1,
3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis-
(4'-Hydroxy-3'-t-butylphenyl) butyric acid @ glycol ester.

As the amine antioxidant, for example, 1
-Naphthylamine, phenyl-1-naphthylamine, p
-Naphthylamine-based antioxidants such as -octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine and phenyl-2-naphthylamine; N, N'-diisopropyl-p-phenylenediamine , N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl- p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-
1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine,
Phenylenediamine antioxidants such as phenylhexyl-p-phenylenediamine and phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p,
p'-di-t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyldiphenylamine, p , P '
-Distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine, and other diphenylamine-based antioxidants; phenothiazine, N And phenothiazine-based antioxidants such as -methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazine carboxylate, and phenoselenazine.

Examples of the sulfur-based antioxidants include dioctylthiodipropionate, didecylthiodipropionate, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, laurylstearylthiopionate. Dipropionate, dimyristylthiodipropionate, distearyl-β,
β'-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-stearyl Thiopropionic acid) pentaerythritol tetraester, (3
-Oleylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid)-
4,4'-thiodi (3-methyl-5-t-butyl-4-
Phenol) ester, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-
Benzimidazole disulfide, dilauryl sulfide, amylthioglycolate and the like. (D
6) A preferable amount of the component is 0.1 to the lubricating base material.
It is about 01 to 5% by mass.

The organometallic compound (D7) improves wear resistance and antioxidant properties. However,
Those corresponding to the component (B) shall be excluded. Specifically, for example, metal dithiophosphate, metal dithiocarbamate, metal salt of mercaptobenzothiazole, metal salt of mercaptobenzimidazole, metal salt of benzamidothiophenol and the like can be mentioned. Examples of the metal atom include lithium, sodium, potassium, magnesium,
Calcium, barium, titanium, zinc, lead, tin, iron,
Cadmium, cobalt, nickel, manganese, strontium, vanadium, copper, antimony, bismuth, tungsten and the like can be mentioned. The preferable blending amount of the component (D7) is about 0.01 to 5% by mass based on the lubricating base material.

The component (D8) is an oiliness improver containing no metal, phosphorus and sulfur atoms. For example, hexanoic acid, octanoic acid, pelargonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid, fatty acids such as linolenic acid; olive oil,
Cocoa butter, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, shea nut oil, cinnamon oil, soybean oil, teaseed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, Sunflower oil, cottonseed oil, coconut oil, wood wax, peanut oil, horse fat, tallow, beef tallow, beef tallow,
Fats and oils such as lard, goat's fat, sheep's fat, milk fat, fish oil and whale oil or hydrides or partially saponified products thereof; epoxidized soybean oil, epoxidized linseed oil and other epoxidized oils and fats; butyl epoxystearate, epoxystearic acid Epoxy esters such as octyl; dibasic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, and dimer acid; ricinoleic acid (castor oil fatty acid), 12-hydroxystearic acid A polycondensate of hydroxystearic acid or an ester of the polycondensate with a fatty acid;

Higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol and behenyl alcohol; higher amines such as laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine and behenylamine; laurylamide, Higher amides such as myristylamide, palmitylamide, stearylamide, oleylamide, and behenylamide; diethanolamides such as lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, stearyl diethanolamide, oleyl diethanolamide, and behenyl diethanolamide; hexane Acid mono /
Di / triglyceride, octanoic acid mono / di / triglyceride, decanoic acid mono / di / triglyceride, lauric acid mono / di / triglyceride, myristic acid mono / di / triglyceride, palmitic acid mono / di / triglyceride, stearic acid mono / di / Glycerides such as triglyceride, oleic acid mono / di / triglyceride, behenic acid mono / di / triglyceride, etc .; polyglycerin hexanoate, polyglyceryl octanoate, polyglycerin decanoate, polyglycerol laurate, polyglycerol myristate Polyglycerol esters such as polyglycerin palmitate, polyglycerin stearate, polyglycerin oleate, polyglycerin behenate;

Sorbitan hexanoate, sorbitan octoate, sorbitan decanoate,
Sorbitan esters such as sorbitan laurate ester, sorbitan myristate ester, sorbitan palmitate ester, sorbitan stearate ester, sorbitan oleate ester and sorbitan behenate ester; (poly) glycerin monooctyl ether;
(Poly) glycerin ethers such as (poly) glycerin monodecyl ether, (poly) glycerin monolauryl ether, (poly) glycerin monooleyl ether, (poly) glycerin monostearyl ether; ethylene oxide, propylene oxide, dodecane Those to which an α-olefin oxide such as -1,2-oxide is added are exemplified. The preferable blending amount of the component (D8) is about 0.05 to 10% by mass based on the lubricating base material.

The component (D9) is a rust preventive. For example,
Sulfonate, sodium nitrite, calcium oxide paraffin wax, magnesium oxide paraffin wax, alkali metal salt of tallow fatty acid, alkaline earth metal salt or amine salt, alkenyl succinic acid or alkenyl succinic acid half ester (exemplified as the above metal detergent) Alkenyl group has a molecular weight of about 100 to 300), sorbitan monoester, pentaerythritol monoester, glycerin monoester, nonylphenol ethoxylate, lanolin fatty acid ester, and lanolin fatty acid calcium salt. The preferred amount of the component (D9) is about 0.1 to 15% by mass based on the lubricating base material.

The component (D10) is a viscosity index improver.
For example, poly (C1-18) alkyl methacrylate,
(C1-18) alkyl acrylate and (C1-18)
Copolymer of alkyl methacrylate, copolymer of diethylaminoethyl methacrylate and (C1-18) alkyl methacrylate, copolymer of ethylene and (C1-18) alkyl methacrylate, polyisobutylene, polyalkylstyrene, copolymer of ethylene and propylene And a copolymer of styrene and maleic acid ester, a copolymer of styrene and maleic amide, a hydrogenated copolymer of styrene and butadiene, and a hydrogenated copolymer of styrene and isoprene. The average molecular weight is 10,000 to 1,50
It is about 0000. The preferable blending amount of the component (D10) is about 0.1 to 20% by mass based on the lubricating base material.

The component (D11) is a metal deactivator. For example, N, N'-salicylidene-1,2-propanediamine, alizarin, tetraalkylthiuram disulfide, benzotriazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, N -Dialkyldithiocarbamoyl) benzothiazole, 2,5-bis (alkyldithio) -1,3,4-thiadiazole,
2,5-bis (N, N-dialkyldithiocarbamoyl) -1,3,4-thiadiazole and the like.
The preferred blending amount of the component (D11) is about 0.01 to 5% by mass based on the lubricating base material.

The component (D12) is an antifoaming agent. For example, polydimethyl silicone, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy / propoxylate, fatty acid ethoxy / propoxylate, sorbitan partial fatty acid ester and the like can be mentioned. The preferable blending amount of the component (D12) is about 0.001 to 1% by mass based on the lubricating base material.

The component (D13) is a solid lubricant. For example, graphite, molybdenum disulfide, polytetrafluoroethylene, fatty acid alkaline earth metal salts, mica, cadmium dichloride, cadmium diiodide, calcium fluoride, lead iodide, lead oxide, titanium carbide, titanium nitride, aluminum silicate , Antimony oxide, cerium fluoride, polyethylene, diamond powder, silicon nitride, boron nitride fluorocarbon, melamine isocyanurate and the like. The preferable blending amount of the component (D13) is about 0.005 to 2% by mass based on the lubricating base material.

One or more of the above-mentioned component (D) can be appropriately added to the lubricating composition of the present invention. When the lubricating composition of the present invention is used as a lubricating oil for an internal combustion engine, at least one of (D1) a metal detergent, (D2) an ashless dispersant, and (D6) an antioxidant is blended. Is preferred.

The lubricating base material which can be used in the present invention is a lubricating base oil composed of mineral oil, synthetic oil or a mixture thereof, and a base grease prepared by blending a thickener with such a lubricating base oil. However, when used as an aqueous lubricating oil, water is used as a base material. When the lubricating composition of the present invention is used as a lubricating oil, the kinematic viscosity of the lubricating base oil is not particularly limited, but is preferably 1 to 50 mm ² at 100 ° C.
/ S at 40 ° C. and about 10 to 1,000 mm ² / s, and the viscosity index (VI) is preferably 100 or more, more preferably 120 or more, and most preferably 135 or more.

The mineral oil used as the base oil of the lubricating composition of the present invention is separated from natural crude oil, and is produced by appropriately distilling, purifying, etc. Mineral oil is mainly composed of hydrocarbons (mostly paraffins), and also contains monocyclic naphthenes, bicyclic naphthenes, aromatics, and the like. Base oils which have been subjected to hydrorefining, solvent dewaxing, solvent extraction, solvent dewaxing, hydrogen dewaxing, catalytic dewaxing, hydrocracking, alkali distillation, sulfuric acid washing, clay treatment, etc. are also preferably used. be able to. These purification means are appropriately combined, and it is effective to repeat the same treatment in a plurality of stages. For example, (A)
A method of subjecting a distillate to a solvent extraction treatment, or a solvent extraction treatment, followed by a hydrogenation treatment, followed by sulfuric acid washing, (B) a method of subjecting a distillate oil to a hydrogenation treatment and then a dewaxing treatment, (C) a distillate A method of hydrotreating oil after solvent extraction,
(D) a method in which distillate is subjected to solvent extraction and then clay treatment, (E) a distillate is subjected to two-stage or three-stage or more hydrogenation, or a subsequent alkali distillation or sulfuric acid washing treatment, F) a method of subjecting a distillate to hydrotreating or hydrotreating, followed by alkali distillation or sulfuric acid washing;
Alternatively, a method of mixing these treated oils is effective.

By performing these treatments, it is possible to remove aromatic components, sulfur content, nitrogen content and the like in the unrefined mineral oil. According to the present technology, these impurities can be removed to a trace amount or less, but the aromatic component has an effect of making the lubricating oil additive easy to dissolve. There is also. For example, the sulfur content and the nitrogen content in the currently used highly refined mineral oil are 0.01% by mass or less, and in some cases 0.005% by mass or less.
On the other hand, the content of the aromatic component is 1% by mass or less, and in some cases, the content is 0.1% by mass.
Some of them have a content of not more than 05% by mass and others have a content of about 3% by mass.

The synthetic oil used as the base oil of the lubricating composition of the present invention is a chemically synthesized lubricating oil such as poly-α-olefin, polyisobutylene (polybutene), diester, Examples thereof include polyol esters, aromatic polycarboxylic acid esters, phosphoric acid esters, silicate esters, polyalkylene glycols, polyphenyl ethers, silicones, fluorinated compounds, and alkylbenzenes. Among them, poly-α-olefin, polyisobutylene (polybutene), diester,
Polyol esters, polyalkylene glycols, and the like can be used for general purposes, and can be preferably used for internal combustion engine oils, processing oils, and the like.

As the poly-α-olefin, for example,
Examples thereof include those obtained by polymerizing or oligomerizing 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, and 1-tetradecene, and those obtained by hydrogenating them. Examples of the diester include dibasic acids such as glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecane diacid, and diesters of alcohols such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol. Examples of the polyol ester include neopentyl glycol, trimethylolethane, trimethylolpropane,
Glycerin, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, or a polyol such as an alkylene oxide adduct thereof, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, capric acid, caproic acid, caprylic acid And esters with fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, mono- or dimethyl ether of a block or random copolymer of ethylene oxide / propylene oxide, and the like.

Each of these synthetic oils is chemically synthesized and therefore is a single substance or a mixture of homologues. Therefore, for example, synthetic oils such as poly-α-olefins, polyisobutylene (polybutene), diesters, polyol esters, and polyalkylene glycols include benzene which is an impurity contained in mineral oil, polycyclic condensed aromatic components, thiophene , And nitrogen such as indole and carbazole are not included.

When used as a grease, a thickener is mixed with the above lubricating base oil to form a base grease. As the thickener, for example, organic non-soaps such as soap-based or complex soap-based thickeners, terephthalamate-based thickeners, urea-based thickeners, polytetrafluoroethylene, fluorinated ethylene-propylene copolymer and the like And a non-soap inorganic thickener. These thickeners may be used alone or in combination of two or more. The amount of the thickener is not particularly limited, but is usually preferably 3 to 40% by mass, more preferably 5 to 20% by mass, based on the base grease comprising the base oil and the thickener. The consistency of the base grease comprising the base oil and the thickener is not particularly limited, but is usually about 100 to 500.

The alkali metal content in the lubricating composition of the present invention is preferably not more than 0.02% by mass in terms of the total alkali metal content contained in the lubricating composition.
It is more preferable that the content be 01% by mass or less. When the alkali metal is mixed in the lubricating composition, the case where the alkali metal is used as a catalyst, a raw material, etc. in the separation, purification, and synthesis steps of the base oil is generally not completely removed. Is mentioned. In addition, also in the process of synthesizing a lubricating oil additive, an alkali metal or a salt thereof is often used as a raw material or a catalyst, and there are cases where they are not completely removed. Sulfur oxymolybdenum dithiocarbamate and sulfurized oxymolybdenum dithiophosphate often use an inorganic material containing an alkali metal during the production process. Furthermore, sodium nitrite or sodium sulfonate is used as a rust inhibitor,
A case where an alkali metal compound is added as a cleaning dispersant is also included.

The nitrogen content in the lubricating composition of the present invention is 0.01% in terms of the total amount of nitrogen contained in the lubricating composition.
It is preferably at least 0.03% by mass, more preferably at least 0.03% by mass, most preferably at least 0.05% by mass. The case where nitrogen is contained in the lubricating composition means that, for example, as the component (A), the general formula (1)
The use of a sulfurized oxymolybdenum dithiocarbamate represented by the following formula, the use of an amine-based antioxidant as an antioxidant, the use of a dithiocarbamate derivative, the use of a fatty acid amide, and the like.

The lubricating composition of the present invention can be used for lubrication in any applications. For example, industrial lubricating oils,
Turbine oil, machine oil, bearing oil, compressor oil, hydraulic oil, hydraulic oil, internal combustion engine oil, refrigeration oil, gear oil, oil for automatic transmission (ATF), oil for continuously variable continuously variable transmission (CVTF), transformer Axle fluids, metal working oils and the like. or,
Plain bearings, rolling bearings, gears, universal joints, torque limiters, constant velocity joints for automobiles (CV
J), and can be used by adding to various greases such as ball joints, wheel bearings, constant speed gears, and transmission gears. The most preferred use of the lubricating composition of the present invention is as a lubricating oil for internal combustion engines such as gasoline engines and diesel engines.

[0087]

The present invention will be described more specifically with reference to the following examples. In the following examples, parts, ppm, and% are based on mass unless otherwise specified. A lubricating oil composition for an internal combustion engine according to the present invention was prepared by using the lubricating base oil, the component (A), the component (B) and the component (C) described below and blending them into the compositions shown in Table 1 below. And a comparative lubricating oil composition were prepared, the amount of molybdenum in the deteriorated oil of these lubricating oil compositions was measured, and their long drainability was evaluated.

(I) Lubricating base oil Base oil 1: Mineral oil-based high VI oil. Kinematic viscosity 4.1 mm ^{2 / s (} 100 ° C.), 18.3 mm ²
/ S (40 ° C.), viscosity index (VI) = 126 Synthetic oil consisting of 80% of poly-α-olefin obtained by oligomerization of base oil 2: 1-decene and 20% of polyol ester. Kinematic viscosity 4.0 mm ^{2 / s (} 100 ° C.), 16.9 mm ²
/ S (40 ° C.), viscosity index (VI) = 138 Base oil 3: A mixed base oil obtained by mixing base oil 1 and base oil 2 at a ratio of 1: 1.

(Ii) Component (A) (A-1): In the general formula (1), R ^{1 to} R ⁴ = 2-ethylhexyl group, S / O of X ^{1 to} X ⁴ = 2.0 / 2. MoDTC which is 0. (A-2): In the general formula (1), R ¹ = R ² = 2-ethylhexyl group, R ³ = R ⁴ = isotridecyl group, X ¹ to
S / O = 2.0 / 2.0 in a MoDTC of X ^4. (A-3): In the general formula (1), R ^{1 to} R ⁴ = Mo where S / O of an isotridecyl group X ^{1 to} X ⁴ is 2.0 / 2.0.
DTC. (A-4): In the general formula (1), R ^{1 to} R ^{4 are} octadecyl groups, and S / O of X ^{1 to} X ⁴ is 2.0 / 2.0 Mo.
DTC. (A-5): MoDTP in the general formula (2), wherein R ^{5 to} R ⁸ = 2-ethylhexyl group X ^{5 to} X ⁸ , S / O = 2.0 / 2.0. (A-6): In the general formula (2), R ^{5 to} R ⁸ = MoD in which S / O of the octadecyl group X ^{5 to} X ⁸ is 2.0 / 2.0.
TP. (A-7): In the general formula (2), R ⁵ = R ⁶ = 2-ethylhexyl group, R ⁷ = R ⁸ = isotridecyl group, X ⁵ to
S / O = 2.0 / 2.0 and is MoDTP of X ^8. In addition, the isotridecyl group is a group derived from isotridecyl alcohol synthesized by doxo on dodecene obtained by trimerizing isobutene.

(Iii) Component (B) (B-1): a fatty acid zinc salt obtained by reacting a mixed fatty acid of 2-ethylhexanoic acid and isotridecanoic acid with zinc oxide at 200 ° C. (B-2): 120 g of 2-ethylhexanoic acid and zinc oxide
Fatty acid zinc salt reacted at ℃. (B-3): a fatty acid molybdenum salt obtained by reacting 2-ethylhexanoic acid and molybdenum trioxide at 200 ° C. (B-4): a fatty acid zinc salt obtained by reacting a mixed fatty acid of 2-ethylhexanoic acid and isotridecanoic acid with molybdenum trioxide at 200 ° C. (B-5): Naphthenic acid and molybdenum trioxide at 200 ° C.
Molybdenum naphthenate reacted with the above. (B-6): Oleic acid and molybdenum trioxide at 200 ° C.
The molybdenum fatty acid salt reacted with the above. (B-7): a fatty acid zinc salt obtained by heating isotridecanoic acid and zinc oxide at 120 ° C. and then performing dehydration under reduced pressure. (B-8): Isotridecanoic acid and molybdenum trioxide in 2
Molybdenum fatty acid salt reacted at 00 ° C.

(Iv) Component (C) (C-1): In the general formula (4), R ¹¹ = R ¹² = 2-
ZDTP wherein the ethylhexyl group, neutral salt / basic salt = 95/5. (C-2): In the general formula (4), R ¹¹ = R ¹² = secondary propyl group and secondary hexyl group, neutral salt / basic salt =
ZDTP that is 95/5. (C-3): ZDTP wherein R ¹¹ = R ¹² = dodecyl group and neutral salt / basic salt = 95/5 in the general formula (4).

(V) Test of residual amount of molybdenum in deteriorated oil The lubricating oil composition for an internal combustion engine of the present invention shown in Table 1 below and the lubricating oil composition of a comparative product were measured according to JIS-K-2274.
According to the following, the temperature was reduced to 130 ° C. for 24 hours at 1,350 rpm by oxidation, and the amount of molybdenum in each of the compositions before and after the deterioration was measured by high performance liquid column chromatography. Molybdenum residual ratio after degradation with respect to the composition before degradation (%)
I asked. Table 1 shows the results.

[0093]

[Table 1]

[0094]

The effect of the present invention is to provide a lubricating composition excellent in so-called long drain properties, which can maintain the friction reducing action even after long-term use. The lubricating composition of the present invention is particularly suitable for use as an engine oil for gasoline engines, diesel engines and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10N 10:12 C10N 10:12 30:02 30:02 30:04 30:04 30:06 30:06 30 : 10 30:10 30:12 30:12 30:14 30:14 30:18 30:18 40:25 40:25 50:08 50:08 (72) Inventor Yoko Saito 7-2 Higashiogu, Arakawa-ku, Tokyo No. 35 F-term in Asahi Denka Kogyo Co., Ltd. (reference) 4H104 AA13R BB16C BB16R BB26C BB26R BE02C BE06C BE07C BG02C BG04C BG10C BG12C BH02C BH03C BH06C BH07C BH11C DB01C EB03 LA03 FA03 LA05

Claims (4)

[Claims] An organic molybdenum compound as a component (A) (excluding a component corresponding to the component (B)); and a fatty acid or naphthenic acid as a component (B) and molybdenum. Or a reaction product of zinc or an oxide thereof; 2. The organic molybdenum compound as the component (A) is represented by the following general formula (1): (Wherein, R ^{1 to} R ⁴ represent a hydrocarbon group, and X ^{1 to} X ⁴ represent a sulfur atom or an oxygen atom), and a sulfurized oxymolybdenum dithiocarbamate represented by the following general formula (2): ] (Wherein, R ⁵ to R ⁸ represents a hydrocarbon group, X ⁵ to X ⁸ is sulfur atom or an oxygen atom.) Molybdenum oxysulfide dithiophosphate represented by, or the following general formula (3) R ⁹ —NH—R ¹⁰ (3) (wherein R ⁹ and R ¹⁰ represent a hydrogen atom or a hydrocarbon group, but are not hydrogen atoms at the same time) and a pentavalent or hexavalent molybdenum The lubricating composition according to claim 1, which is a reaction product with a compound having an atom. Further, as the component (C), the following general formula (4): (Wherein, R ¹¹ and R ¹² represent a hydrocarbon group, and a is 0 to 0)
Represents 1/3 number. 3. The lubricating composition according to claim 1, which comprises a zinc dithiophosphate represented by the formula: 4. The following components (D1) to (D13): (D1) a metal detergent (D2) an ashless dispersant (D3) a compound containing a phosphorus atom (D4) a compound containing a phosphorus atom and a sulfur atom (D5) Compound containing a sulfur atom and not containing a metal atom (D6) Antioxidant (D7) Organometallic compound (however, excluding those falling under the component (B)) (D8) Metal atom, phosphorus atom And oiliness improver containing no sulfur atom (D9) Rust inhibitor (D10) Viscosity index improver (D11) Metal deactivator (D12) Defoamer (D13) Solid lubricant The lubricating composition according to any one of claims 1 to 4, further comprising: