JP2003105367A - Lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricant composition having friction-reducing activities even in an initial time of the use. SOLUTION: This lubricant composition contains (A) an oil-soluble molybdenum compound, (B) a solid lubricant and (C) an ashless dispersant in a lubricant base oil.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lubricating composition.

[0002]

2. Description of the Related Art At present, the circumstances surrounding automobiles are becoming stricter such as fuel consumption regulations and exhaust gas regulations. Behind this is environmental protection such as global warming, air pollution, and acid rain, and resource protection from concerns about the limited exhaustion of petroleum energy. Improving fuel efficiency is currently the most effective measure against these problems.

In order to reduce the fuel consumption of automobiles, the weight of automobiles is improved, the engine is improved, and the like, as well as the automobile itself is improved and the viscosity of engine oil is reduced to prevent friction loss in the engine, and a good friction modifier. Improvement of engine oil, such as addition of oil, 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 portion, friction loss can be reduced by lowering the viscosity of the engine oil. Therefore, in recent years, the viscosity of engine oil has been reduced, but the problems of deterioration of sealing property and increase of wear amount have newly occurred due to the reduction of viscosity.
In addition, engine oil plays an important role in lubrication of valve trains, bearings, etc., but since there is much mixed lubrication and boundary lubrication in this part, lowering the viscosity of engine oil causes increased wear. ing. Therefore, a friction modifier, an extreme pressure agent and the like have been added for the purpose of reducing friction loss due to a decrease in viscosity of engine oil and preventing wear.

Since the organic molybdenum compound has an excellent friction reducing action, it is added to various lubricating oils.
However, the friction-reducing action of the organic molybdenum compound is not sufficient at the initial stage of use, and there is a tendency that an excellent friction-reducing action is exhibited after a lapse of some time from the start of use. Therefore, for example, when an engine oil containing an organic molybdenum compound is used, a rapid friction reducing effect at the time of starting cannot be obtained. It was necessary to start the vehicle after "driving" in order to bring out the performance of the organomolybdenum compound, and there were some unsatisfactory aspects from the environmental issues.

By the way, a dispersant is used in engine oil for the purpose of dispersing sludge and the like, and it is used in combination with an organic molybdenum compound (JP-A-59-12259).
No. 7, JP-A-62-240388, JP-A-1
1-246883 gazette, etc.) have been reported,
There is nothing related to the immediate friction reduction effect at startup.

[0006] In addition, a solid lubricant such as graphite or molybdenum disulfide is often used as the grease, and a grease in which such a solid lubricant and an organic molybdenum compound are used in combination (JP-A-4-304300 and JP-A-5-304). Two
30486, JP-A-8-170091, etc.)
Although many have been reported, there is nothing related to the rapid friction reduction effect at startup.

[0007]

A method for compensating for such a disadvantage of the organic molybdenum compound that it cannot exhibit a sufficient friction reducing effect in the initial stage of use has not been known so far.
It has been a subject of a lubricating composition containing an organic molybdenum compound.

Therefore, an object of the present invention is to provide a lubricating composition having a friction reducing effect even in the initial stage of use.

[0009]

Therefore, the inventors of the present invention diligently studied, and by using an organic molybdenum compound, a solid lubricant and an ashless dispersant together,
The inventors have found that a lubricating composition having a friction reducing effect can be obtained, and completed the present invention.

That is, in the present invention, the lubricating base material contains the oil-soluble molybdenum compound as the component (A), the solid lubricant as the component (B), and the ashless dispersant as the component (C). It relates to a lubricating composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the lubricating composition of the present invention,
The component (A) is an organic molybdenum compound. Examples of the organic molybdenum compound include fatty acid molybdenum salt, sulfurized oxymolybdenum xanthate, a reaction product of molybdenum trioxide and an acidic phosphoric acid ester, a reaction product of molybdenum trioxide and a fatty acid diethanolamide, and a molybdenum trioxide and an alkylalkanolamine. The reaction product, a reaction product of molybdenum trioxide and glycerin monofatty acid ester, succinimide, a carboxylic acid amide or a Mannich base or a reaction product of these boride and molybdenum trioxide, and the like, preferable organic molybdenum compounds,
General formula (1)

[Chemical 4] Oxymolybdenum dithiocarbamate represented by the general formula (2)

[Chemical 5] A sulfurized oxymolybdenum dithiophosphate represented by or a general formula (3)

Embedded image A molybdenum amine reaction product, which is a reaction product of an amine represented by R ⁹ —NH—R ¹⁰ (3) and a compound having a pentavalent or hexavalent molybdenum atom, and more preferably the general formula It is a sulfurized oxymolybdenum dithiocarbamate represented by (1).

In the general formulas (1) to (3), R ^{1 to} R
¹⁰ is a hydrocarbon group, for example, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group, or the like. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Secondary butyl, tert-butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tert-pentyl, hexyl, secondary hexyl, isoheptyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, 2
Octyl, isooctyl, nonyl, secondary nonyl, isononyl, decyl, isodecyl, secondary decyl, undecyl, secondary undecyl, isoundecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl ,
Secondary hexadecyl, stearyl, isostearyl, 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,
Examples include 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 group and the like can be mentioned. Examples of cycloalkyl groups and cycloalkenyl groups include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl groups, etc. Is mentioned. still,
R ⁹ and R ¹⁰ may be hydrogen atoms, but they are not hydrogen atoms at the same time.

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 from each other. In particular, when R ^{1 to} R ⁴ are different from each other, it is preferable in order to prolong the drain (long life) of the lubricating composition.

Of these, R ^{1 to} R ¹⁰ are preferably an alkyl group, an alkenyl group or an aryl group. More specifically, R ^{1 to} R ⁴ , that is, a sulfurized oxymolybdenum dithiocarbamate has an alkyl group having 8 to 13 carbon atoms, and R ^{5 to} R ⁸ , that is, a sulfurized oxymolybdenum dithiophosphate, has 6 to 6 carbon atoms. An alkyl group of 13 and R ^{9 to} R ¹⁰ , that is, an alkyl group having 6 to 18 carbon atoms is preferable in the molybdenum amine reaction product. this is,
This is because if the carbon number is too small, the oil solubility becomes poor, and if the carbon number is too large, the melting point becomes high, the handling becomes poor, and the activity becomes low.

Further, in the general formulas (1) and (2),
X ^{1 to} X ⁴ and X ^{5 to} X ⁸ are each a sulfur atom or an oxygen atom, and all of X ^{1 to} X ⁴ , X ^{5 to} X ⁸ may be a sulfur atom or an oxygen atom, and four X ¹ To X ⁴ and X ^{5 to} X ⁸ may each be a sulfur atom or an oxygen atom, but in consideration of lubricity and corrosiveness, the abundance ratio of sulfur atom / oxygen atom is 1
Particularly preferably, it is / 3 to 3/1.

The pentavalent or hexavalent molybdenum compound reacted with the amine represented by the general formula (3) is, for example, molybdenum trioxide or its hydrate (MoO ₃ .nH _2).
O), molybdic acid (H ₂ MoO ₄ ), alkali metal molybdate (M ₂ MoO ₄ ), ammonium molybdate ((NH ₄ ) ₂ MoO ₄ or (NH ₄ ) ₆ [Mo ₇ O ₂₄ ] .4
H ₂ O), MoCl ₅ , MoOCl ₄ , MoO ₂ Cl ₂ , M
Examples thereof include oO ₂ Br ₂ , Mo ₂ O ₃ Cl _{6, and the} like. In consideration of the yield of molybdenum-nitrogen compound, a hexavalent molybdenum compound is preferable. Among the hexavalent molybdenum compounds, easily available molybdenum trioxide or its hydrate, molybdic acid, alkali metal molybdate, ammonium molybdate and the like are preferable.

As the component (A), a sulfurized oxymolybdenum dithiocarbamate represented by the general formula (1), a sulfurized oxymolybdenum dithiophosphate represented by the general formula (2), or an amine represented by the general formula (3) and 5 Use of only one of the molybdenum amine reactants, which is a reactant of a compound having a valent or hexavalent molybdenum atom,
Two or more kinds may be used in combination, but it is preferable to use at least one sulfurized oxymolybdenum dithiocarbamate represented by the general formula (1).

The addition amount of the component (A) is not particularly limited, but if the addition amount is too small, the friction reducing effect is not sufficient, and if the addition amount is too large, it tends to cause sludge and corrosion. Therefore, when the lubricating base material is a lubricating base oil, the amount of the component (A) added is preferably 0.001 to 3 mass% in molybdenum amount, more preferably 0.
005 to 2% by mass, more preferably 0.01 to 1% by mass
When the lubricating base material is a base grease, the amount of molybdenum is preferably 0.002 to 5% by mass, more preferably 0.004 to 4% by mass, and even more preferably 0.00.
It is from 02 to 3% by mass.

In the lubricating composition of the present invention, the component (B) is a solid lubricant. Examples of solid lubricants include graphite, molybdenum disulfide, tungsten disulfide, and polytetrafluoroethylene (PTF).
E), polyamide (nylon), polyethylene, polyacetal, polyimide, fatty acid alkaline earth metal salt, mica, cadmium dichloride, cadmium diiodide, lead iodide, lead oxide, molybdenum trioxide, titanium carbide, aluminum silicate, oxidation Antimony, calcium fluoride,
Examples thereof include barium fluoride, cerium fluoride, carbon fluoride, diamond powder, titanium nitride, silicon nitride, boron nitride, carbon fluoride and melamine isocyanurate.
Of these solid lubricants, graphite and molybdenum disulfide are preferred, with graphite being most preferred.

The addition amount of the component (B) is not particularly limited, but if the addition amount is too small, the effect of reducing the friction at the initial stage of use is not sufficient, and if the addition amount is too large, the lubricating base material is particularly lubricating base oil. When it is, the component (B) may be separated or precipitated. Therefore, the preferable blending amount of the component (B) is 0.001 to 10% by mass, more preferably 0.002 to 5% by mass, and most preferably 0.005 to 2% by mass relative to the lubricating base material. It is% by mass.

In the lubricating composition of the present invention, the component (C) is an ashless dispersant. Examples of the ashless dispersant include succinimide, benzylamine, succinic acid ester, and boron-modified products thereof. As the succinimide, for example, the following general formula (4)

[Chemical 7] (R represents a polyalkenyl group such as a polybutenyl group and n represents a number of about 1 to 10), or the following general formula (5).

[Chemical 8] (R represents a polyalkenyl group such as a polybutenyl group, and n represents a number of about 1 to 10.) and the like. The molecular weight of the polyalkenyl group is usually 300 to 4,0.
It is about 00. Further, n is preferably 2-5.

As the benzylamine (Mannich reaction product), for example, the following general formula (6) is used.

[Chemical 9] (R represents a polyalkenyl group such as a polybutenyl group, and n represents a number of about 1 to 10) and the like. The molecular weight of the polyalkenyl group is usually 300 to 4,0.
It is about 00. Further, n is preferably 2-5.

Examples of the succinic acid ester include those represented by the following general formula (7)

[Chemical 10] (R represents a polyalkenyl group such as a polybutenyl group, and R'represents a residue obtained by removing one hydroxyl group from monool or polyol.) Or the following general formula (8).

[Chemical 11] (R represents a polyalkenyl group such as a polybutenyl group, and R ′ represents a residue obtained by removing two hydroxyl groups from a polyol.) And the like. The molecular weight of the polyalkenyl group is usually about 300 to 4,000.

The boron-modified products of the above compounds include
For example, the following substituent (9) is added to the arrow portion of the above general formula.

[Chemical 12] Or the following general formula (10)

[Chemical 13] And the like.

Among these ashless dispersants, preferred as the component (C) is succinimide or its boron modified product, and the monosuccinimide represented by the general formula (4) is particularly preferred. The addition amount of the ashless dispersant as the component (C) is not particularly limited, but if the addition amount is too small, the friction reducing effect at the initial stage of use is not sufficient, and if the addition amount is too large, the friction reducing effect is hindered. There is.
Therefore, the preferable blending amount of the component (C) is about 0.5 to 10% by mass with respect to the lubricating base material.

Further, in the lubricating composition of the present invention, (D1) a metal detergent; (D2) a compound containing a phosphorus atom; (D3) a compound containing a phosphorus atom and a sulfur atom, depending on the purpose of use. (D4) a compound containing a sulfur atom and containing no metal atom; (D5) an antioxidant; (D6) an organometallic compound; (D7) an oiliness improver containing no metal atom, phosphorus atom or sulfur atom; D8) rust preventive agent; (D9) viscosity index improver; (D10) metal deactivator; (D11) antifoaming agent and the like can be used in combination.

Examples of the metal detergent (D1) include metal sulfonates, metal phenates, metal salicylates,
Examples include metal phosphonates. Examples of the metal sulfonate include (mono or di) alkylbenzene sulfonic acid metal salt, (mono or di) alkylnaphthalene sulfonic acid metal salt, petroleum sulfonic acid metal salt and the like.
Examples of the metal phenate include (mono or di) alkylphenol metal salts, thiobis {(mono or di) alkylphenol} metal salts, methylenebis {(mono or di) alkylphenol} metal salts and the like. Examples of the metal salicylate include (mono or di) alkyl salicylic acid metal salt, thiobis {(mono or di) alkyl salicylic acid} metal salt, methylenebis {(mono or di)
Alkyl salicylic acid} metal salts and the like can be mentioned. The metal atom is preferably an alkali metal or an alkaline earth metal, more preferably calcium, magnesium or barium. Further, the above compound is generally a neutral salt, but as a metal detergent, a neutral or basic salt obtained by basifying the neutral salt with a metal oxide or a metal hydroxide while blowing carbon dioxide. Overbased ones are preferably used.
Overbased products are usually contained in the form of carbonates.
The total base number (TBN) of these basic or overbased metal detergents is generally about 100 to 500 mgKOH / g. Most preferred of these metal detergents are neutral, basic or overbased calcium salicylates or calcium sulfonates. (D
The preferable blending amount of the component (1) is 0.
It is about 5 to 15 mass%.

Examples of the compound (D2) containing a phosphorus atom include organic phosphorus compounds such as phosphine, phosphine oxide, phosphinite, phosphonite, phosphinate, phosphite, phosphonate, phosphate, and phosphoramidate. These compounds mainly improve lubricity, wear resistance, etc., but may also act as an antioxidant. Examples of the organic phosphine represented by (R) ₃ P include tributylphosphine, trihexylphosphine, trioctylphosphine, tri (2-ethylhexyl) phosphine, trinonylphosphine, tridecylphosphine, trilaurylphosphine, trimyristylphosphine, Examples include tripalmitylphosphine, tristearylphosphine, trioleylphosphine, triphenylphosphine, tricresylphosphine, and the like. (R) ₂ P- (CH ₂ ) _n-
Examples of the alkylidene bisphosphine represented by P (R) ₂ include methylenebis (dibutylphosphine), methylenebis (dihexylphosphine), methylenebis (dioctylphosphine), methylenebis (di2).
-Ethylhexylphosphine), methylenebis (dinonylphosphine), methylenebis (didecylphosphine), methylenebis (dilaurylphosphine), methylenebis (dimyristylphosphine), 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 tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, tri (2-ethylhexyl) phosphine oxide, trinonylphosphine oxide, and tridecylphosphine oxide. , Trilaurylphosphine oxide, trimyristylphosphine oxide, tripalmitylphosphine oxide, tristearylphosphine oxide,
Examples thereof include trioleylphosphine oxide, triphenylphosphine oxide, tricresylphosphine oxide and the like. Examples of the organic phosphite represented by (RO) ₃ P include mono, di, or tri (hereinafter, mono,
The term di or bird is abbreviated as mono / di / tri. ) Butyl phosphite, 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 / J /
Trimyristyl phosphite, mono / di / tripalmityl phosphite, mono / di / tristearyl phosphite, mono / di / trioleyl phosphite, mono / di /
Examples include triphenyl phosphite, mono / di / tricresyl phosphite, and the like. Other phosphites include, for example, pentaerythritol diphosphite,
Examples thereof include pentaerythritol tetraphosphite and alkylidene bisphosphite. (RO) ₃ P = O
Examples of the organic phosphate represented by: mono / di / tributyl phosphate, mono / di / trihexyl phosphate, mono / di / trioctyl phosphate, mono / di / tri (2-ethylhexyl) phosphate, mono / di / trino Nyl 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 /
Examples include di / tricresyl phosphate. Further, a phosphate having a polyoxyalkylene group, for example,
Examples thereof include lauryl alcohol ethylene oxide and / or propylene oxide adduct phosphate. Of these phosphates, mono- or diphosphates are called acidic phosphoric acid esters and may be used after being neutralized with a base such as alkali or amine. Examples of the alkali include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Examples of the amine include ammonia; methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine,
Alkylamines such as di (iso) propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tridecylamine, cetylamine, palm alkylamine, soybean oil-derived alkylamine, tallow-derived alkylamine, 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, N,
Alkanolamines such as N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or their alkylene oxide adducts; N-butyldiethanolamine, N-hexyldiethanolamine, N-octyldiethanolamine, N-decyldiethanolamine, N-coconut. Alkyldiethanolamine, N-soybean oil-derived alkyldiethanolamine, N-beef tallow-derived alkyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, N, N-dibutylmonoethanolamine, N, N-dihexylmonoethanolamine, N, N- Dioctyl monoethanolamine, N, N-didecyl monoethanolamine, N, N
-Bis (coconut alkyl) monoethanolamine, N, N
-Bis (alkyl derived from soybean oil) monoethanolamine,
Examples include N-long-chain alkylalkanolamines such as N, N-bis (beef tallow-derived alkyl) monoethanolamine, N-dioleylmonoethanolamine, N-distearylmonoethanolamine, and their alkylene oxide adducts. . As a phosphoramidate,
The thing etc. which carried out the condensation reaction of the said phosphate and the said amine etc. are mentioned. The preferable blending amount of the component (D2) is
It is about 0.1 to 10 mass% with respect to the lubricating base material.

Examples of the compound (D3) containing a phosphorus atom and a sulfur atom include trithiophosphite and thiophosphate. These compounds mainly improve lubricity, wear resistance, etc., but may also act as an antioxidant. Examples of the organic trithiophosphite represented by (RS) ₃ P include mono / di / tributyltrithiophosphite, mono / di / trihexyltrithiophosphite, mono / di / trioctyltrithiophosphite, and mono / di / Tri (2-ethylhexyl) trithiophosphite, mono / di / trinonyl trithiophosphite, mono / di / tridecyl trithiophosphite, mono / di / trilauryl trithiophosphite, mono / di / trimyristyl trithiophosphite,
Mono / di / tripalmityl trithiophosphite, mono / di / tristearyl trithiophosphite, mono / di / trioleyl trithiophosphite, mono / di / triphenyl trithiophosphite, mono / di / tricresyl trithiophosphite A fight etc. are mentioned. (RO) ₃ P
Examples of the organic thiophosphate represented by ═S include mono / di / tributylthiophosphate, mono / di / trihexylthiophosphate, mono / di / trioctylthiophosphate, mono / di / tri (2-ethylhexyl) thio. Phosphate, 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,
Examples include mono / di / tricresyl thiophosphate. Further, dithiophosphoric acid dimer can also be used.
The preferable blending amount of the component (D3) is about 0.1 to 10% by mass with respect to the lubricating base material.

Examples of the compound (D4) containing a sulfur atom and containing no metal atom include fats and oils such as sulfurized lard, sulfurized fish oil, sulfurized whale oil, sulfurized soybean oil, sulfurized pinene oil, sulfurized gypsum oil, and sulfurized fatty acid. In addition to sulfurized double bonds of the compounds derived from, simple sulfur, organic mono- or polysulfide, sulfides of polyolefin such as isobutylene, 1,
3,4-thiadiazole derivative, thiuram disulfide, dithiocarbamic acid ester and the like can be mentioned. The following general formula (D4-1)

Embedded image As the organic mono- or polysulfide represented by R—S _x —R (D4-1),
For example, dimethyl mono / di / polysulfide, diethyl mono / di / polysulfide, dipropyl mono / di /
Polysulfide, diisopropylmono / di / polysulfide, dibutylmono / di / polysulfide, diisobutylmono / di / polysulfide, ditertiarybutylmono / di / polysulfide, dipentylmono / di / polysulfide, diisopentylmono / di / polysulfide, dineopentyl Mono / di / polysulfide, ditertiary pentyl mono / di / polysulfide, dihexyl mono / di / polysulfide, diheptyl mono / di / polysulfide, dioctyl mono / di /
Polysulfide, di2-ethylhexylmono / di / polysulfide, dinonylmono / di / polysulfide, ditercharinonylmono / 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, diicosylmono / di / polysulfide, didocosylmono / di / polysulfide, ditetracosylmono /
Di / polysulfide, ditriacontyl mono / di / polysulfide, diphenyl mono / di / polysulfide, ditoluyl 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, dicinnamyl mono / di / polysulfide, dibenzhydryl mono / di / polysulfide, ditrityl mono / di / polysulfide, di (ethylphenyl) mono / di / polysulfide, di (propylphenyl) mono / di / polysulfide, di (butyl) Phenyl) mono / di / polysulfide, di (pentylphenyl) mono / di / polysulfide, di (hexylphenyl) mono / di / polysulfide, di (heptylphenyl) 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 / / Polysulfide, di (phenylphenyl) mono / di / polysulfide, di (benzylphenyl) mono / di / polysulfide, di (styrenated phenyl) mono / di / polysulfide, di (p-cumylphenyl) mono / di / polysulfide, di Dicyclohexylmono / di / polysulfide, dicyclohexylmono / di / polysulfide, dicycloheptylmono / di / polysulfide, dimethylcyclopentylmono / di / polysulfide, dimethylcyclohexylmono / di / polysulfide, dimethylcycloheptylmono / di / polysulfide, etc. Hydrocarbyl sulfide; di (ethylhydroxyphenyl) mono / di / polysulfide, di (propylhydroxyphenyl) mono / di / polysulfide, di (butyl) Hydroxyphenyl) 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 / polysulfide, di (undecylhydroxyphenyl) mono / di / polysulfide, di (dodecylhydroxyphenyl) Examples include dihydrocarbylphenol sulfide such as mono / di / polysulfide.

The 1,3,4-thiadiazole derivative has the following general formula (D4-2).

[Chemical 15] (In the formula, 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, 3,4,5,5.
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 can be mentioned, among which 2 to 4 sulfur atoms are continuously bonded. Groups are particularly preferred.

Thiuram disulfide has the following general formula (D4-3).

[Chemical 16] (R represents a hydrocarbon group, R'represents a sulfur atom, a divalent hydrocarbon group or a divalent hydrocarbon group containing a sulfur atom). R'is -S (-S) _n
A group represented by-(n is 0 or a number of 1 or more),
Methylene _{group, -S (-S) n (-CH} 2) n -S (-S) n
Examples thereof include a group represented by-(wherein n is the same or different and is a number of 0 or 1 or more). R is preferably a chain hydrocarbon group having 4 or more carbon atoms.

The dithiocarbamic acid ester has the following general formula (D4-4).

[Chemical 17] (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). The preferable blending amount of the component (D4) is about 0.1 to 15 mass% with respect to the lubricating base material.

Examples of (D5) antioxidants include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants and the like. Examples of the phenolic antioxidant include 2,6-di-tert.-butylphenol (hereinafter, tert.-butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol. ,
2,6-di-t-butyl-4-methylphenol, 2,
6-di-t-butyl-4-ethylphenol, 2,4-
Dimethyl-6-t-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'-butylidene bis (3-methyl-6-t-butylphenol), 4,4'-isopropylidene bis (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-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, stearyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- ( Oleyl 4-hydroxy-3,5-di-t-butylphenyl) propionate, dodecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3, 5-di-t-butylphenyl) decyl propionate, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis {3-
(4-hydroxy-3,5-di-t-butylphenyl)
Propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy-3,
Ester of 5-di-t-butylphenyl) propionic acid and glycerin monooleyl ether, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid butylene glycol ester, 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-t-butyl-4- (N,
N'-dimethylaminomethylphenol), bis (3,
5-di-t-butyl-4-hydroxybenzyl) sulfide, tris {(3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-t-) Butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, bis {2-methyl-4- (3-
n-Alkylthiopropionyloxy) -5-t-butylphenyl} sulfide, 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-t-butyl-4-hydroxyphenyl)} propionate, N, N'-hexamethylenebis ( 3,5-di-t-butyl-4-hydroxy-
Hydrocinamide), 3,5-di-t-butyl-4-hydroxy-benzyl-phosphoric acid diester, bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 3,9-bis [1, 1-dimethyl-2- {β-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10
-Tetraoxaspiro [5,5] undecane, 1,1,
3-tris (2-methyl-4-hydroxy-5-t-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 and the like.
Examples of the amine-based antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1.
-Naphthylamine type antioxidants such as 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, phenylhexyl-p-phenylenediamine, phenyloctyl-
Phenylenediamine antioxidants such as p-phenylenediamine; dipyridylamine, diphenylamine, p,
p'-di-n-butyldiphenylamine, p, p'-di-t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine ,
p, p'-didecyldiphenylamine, p, p'-didodecyldiphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine,
Diphenylamine antioxidants such as 4,4′-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine; phenothiazine, N-methylphenothiazine, N-
Examples thereof include phenothiazine-based antioxidants such as ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester, and phenoselenazine.
Examples of the sulfur-based antioxidant include dioctylthiodipropionate, didecylthiodipropionate, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, laurylstearylthiodipropionate. , Dimyristylthiodipropionate, distearyl-β, β'-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3
-Laurylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) -4,4 ' -Thiodi (3-methyl-5-t-butyl-4-phenol)
Esters, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, amyl thioglycolate and the like can be mentioned. When the lubricating base material is a lubricating base oil, the blending amount of the component (D5) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the lubricating base oil. , And most preferably 0.1 to 2% by mass. When the lubricious base material is a base grease, the amount added is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.5 to 5% by mass relative to the base grease. It is% by mass.

The organometallic compound (D6) improves abrasion resistance and antioxidant properties. Specifically, for example, hexanoic acid, octanoic acid, pelargonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid, linolenic acid and other fatty acids or lithium naphthenic acid. , Sodium, potassium, magnesium, calcium, barium,
Titanium, zinc, lead, tin, iron, cadmium, cobalt,
Examples thereof include nickel, manganese, strontium, titanium, vanadium, copper, antimony, bismuth and tungsten salts. The fatty acid preferably has about 12 to 18 carbon atoms. Further, a metal salt of dithiophosphoric acid, a metal salt of dithiocarbamic acid, a metal salt of mercaptobenzothiazole, a metal salt of mercaptobenzimidazole, a metal salt of benzamidethiophenol and the like can be mentioned. The metal atom is the metal atom exemplified above. The preferable blending amount of the component (D6) is
It is about 0.1 to 5 mass% with respect to the lubricating base material.

The component (D7) is an oiliness improver containing no metal atom, phosphorus atom or sulfur atom. For example, fatty acids such as hexanoic acid, octanoic acid, pelargonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid, linolenic acid; linseed oil, eno oil, eutica oil, olive oil,
Cocoa butter, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, shea nut oil, cinnamon oil, soybean oil, tea seed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, Sunflower oil, cottonseed oil, palm oil, wax, peanut oil, horse fat, beef tallow, beef tallow, beef tallow,
Fats and oils such as pork fat, goat fat, sheep fat, milk fat, fish oil, whale oil and the like, or hydrides or partially saponified products thereof; epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil; butyl epoxystearate, epoxystearic acid Epoxidized esters such as octyl; dibasic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 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; a higher alcohol such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol and behenyl alcohol; laurylamine, myristylamine, palmityl Amine, steer Higher amines such as ruamine, oleylamine, behenylamine; higher amides such as laurylamide, myristylamide, palmitylamide, stearylamide, oleylamide, behenylamide; lauryldiethanolamide, myristyldiethanolamide, palmityldiethanolamide, stearyldiethanolamide. , Diethanolamides such as oleyldiethanolamide and behenyldiethanolamide; hexanoic 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 / triglyceride, oleic acid mono / di / triglyceride, beehive Phosphate mono /
Diglyceride such as di / triglyceride; polyglycerin hexanoate, polyglycerin octanoate, polyglycerin decanoate, polyglycerin lauric acid, polyglycerin myristate, polyglycerin palmitate, polyglycerin stearate, olein Polyglycerin esters such as acid polyglycerin esters and behenic acid polyglycerin esters; hexanoic acid sorbitan ester, octanoic acid sorbitan ester, decanoic acid sorbitan ester, lauric acid sorbitan ester, myristic acid sorbitan ester, palmitic acid sorbitan ester, stearic acid sorbitan ester , Sorbitan oleate, sorbitan behenate, and other sorbitan esters; Poly) glycerin monooctyl ether, (poly) glycerin monodecyl ether,
(Poly) glycerin monolauryl ether, (poly) glycerin monooleyl ether, (poly) glycerin monostearyl ether and other (poly) glycerin ethers; ethylene oxide, propylene oxide, dodecane-1,2-oxide, etc. Examples thereof include those to which α-olefin oxide has been added. (D
The preferable blending amount of the component 7) is 0.
It is about 05 to 15% by mass.

The component (D8) is a rust preventive agent. For example,
Examples of the metal detergent include sulfonate, sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, tallow fatty acid alkali metal salt, alkaline earth metal salt or amine salt, alkenyl succinic acid or alkenyl succinic acid half ester ( The alkenyl group has a molecular weight of about 100 to 300), sorbitan partial fatty acid ester, pentaerythritol partial fatty acid ester, glycerin monoester, nonylphenol ethoxylate, lanolin fatty acid ester, lanolin fatty acid calcium salt and the like. The preferable blending amount of the component (D8) is about 0.1 to 15% by mass with respect to the lubricating base material.

The component (D9) is a viscosity index improver. For example, poly (C1-18) alkyl methacrylate,
(C1-18) Alkyl acrylate / (C1-18)
Alkyl methacrylate copolymer, diethylaminoethyl methacrylate / (C1-18) alkyl methacrylate copolymer, ethylene / (C1-18) alkyl methacrylate copolymer, polyisobutylene, polyalkylstyrene, ethylene / propylene copolymer, styrene /
Maleic acid ester copolymer, styrene / maleic acid amide copolymer, styrene / butadiene hydrogenated copolymer,
Examples thereof include styrene / isoprene hydrogenated copolymer.
The average molecular weight is about 10,000 to 1,500,000. The preferable blending amount of the component (D9) is about 0.1 to 20% by mass with respect to the lubricating base material.

The component (D10) 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 can be mentioned.
The preferable blending amount of the component (D10) is about 0.01 to 5% by mass with respect to the lubricating base material.

The component (D11) is an antifoaming agent. Examples thereof include polydimethyl silicone, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy / propoxylate, fatty acid ethoxy / propoxylate, and sorbitan partial fatty acid ester. The preferable blending amount of the component (D11) is about 0.001 to 1% by mass with respect to the lubricating base material.

The above components (D1) to (D11) are
One kind or two or more kinds can be appropriately mixed. When two or more kinds are blended, at least one kind is preferably an oiliness improver which does not contain (D7) metal atom, phosphorus atom and sulfur atom. Further, among the organic molybdenum compounds of the present invention, since the molybdenum amine compound of the general formula (3) does not contain a sulfur atom, it does not contain a sulfur atom-containing compound, for example, the above-mentioned (D4) sulfur atom. ,
Compounds containing no metal atom, (D3) compounds containing phosphorus atom and sulfur atom, and (D6) organometallic compounds containing sulfur atom, dithiophosphoric acid metal salt, dithiocarbamic acid metal salt, mercaptobenzothiazole metal salt , Mercaptobenzimidazole metal salt, benzamide thiophenol metal salt and the like are preferably blended.

The lubricating base material that can be used in the lubricating composition of the present invention is a base oil composed of mineral oil, synthetic oil or a mixture thereof, or a base oil obtained by blending a thickener with such a base oil. In addition to grease, water is used as the base material when used as an aqueous lubricating oil.

When the lubricating composition of the present invention is used as a lubricating oil, the kinematic viscosity of the base oil is not particularly limited, but preferably 1 to 50 mm ² / sec at 100 ° C. and 10 to 40 ° C.
1,000mm ² / s approximately, viscosity index (VI) is preferably 100 or more, more preferably 120 or more, 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 and refining it. The main component of mineral oil is hydrocarbons (mostly paraffins), and also contains 1-ring naphthenes, 2-ring naphthenes, aromatics and the like. A base oil obtained by subjecting these to hydrorefining, solvent dewaxing, solvent extraction, solvent dewaxing, hydrodewaxing, catalytic dewaxing, hydrocracking, alkaline distillation, sulfuric acid washing, and clay treatment is also preferably used. be able to. These refining means are appropriately combined and performed, and it is also effective to repeat the same treatment in a plurality of stages.

For example, (A) distillate oil is subjected to solvent extraction treatment, or solvent extraction treatment is followed by hydrotreatment, followed by washing with sulfuric acid, (B) distillate oil is hydrotreated and then dewaxing treatment. Method, (C) distillate oil is subjected to solvent extraction treatment followed by hydrogenation treatment, (D) distillate oil is subjected to solvent extraction treatment and then treated with clay, and (E) distillate oil is treated in two or three stages. A method of performing the above-mentioned hydrotreatment, or a method of carrying out an alkali distillation or a sulfuric acid washing treatment thereafter, (F) a method of hydrotreating a distillate oil, or a method of subjecting the distillate oil to a hydrotreatment and then an alkali distillation or a sulfuric acid washing treatment; A method of mixing these treated oils is effective.

By carrying out these treatments, it is possible to remove aromatic components, sulfur content, nitrogen content and the like in the unrefined mineral oil. With the current technology, these impurities can be removed to a trace amount or less, but since the aromatic component has the effect of facilitating the dissolution of the lubricating oil additive, when about 3 to 5% by mass is left. There is also. For example, the sulfur content and nitrogen content in highly refined mineral oil currently used are 0.01 mass% or less, and in some cases, 0.005 mass% or less.
On the other hand, the aromatic component is 1% by mass or less, and in some cases, 0.
Some of them are less than 05% by mass, and some remain 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, for example, poly-α-olefin, polyisobutylene (polybutene), diester. , Polyol esters, aromatic polycarboxylic acid esters, phosphoric acid esters, silicic acid esters, polyalkylene glycols, polyphenyl ethers, silicones, fluorinated compounds, alkylbenzenes, hydrogenated products of terpenes, 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, 1-tetradecene, or hydrogenated products thereof. Examples of diesters include dibasic acids such as glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and alcohol diesters 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 polyols such as alkylene oxide adducts thereof with butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, capric acid, caproic acid, caprylic acid , Lauric acid, myristic acid, palmitic acid, stearic acid, esters with fatty acids such as oleic acid, and the like. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, and ethylene oxide / propylene oxide block or random copolymer mono- or dimethyl ether. Examples of hydrogenated products of terpenes include squalane, which is a hydrogenated product of squalene. In recent years, squalane
In addition to hydrogenation of squalene, it may be chemically synthesized using isoprene as a raw material. Among these, hydrogenated terpenes are preferable, and squalane is most preferable.

Each of these synthetic oils is a single substance or a mixture of homologues because it is chemically synthesized. 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, and thiophene. Etc., sulfur content, etc., indole, carbazole, etc. nitrogen content, etc. are not included.

The base grease is prepared by mixing the above base oil with a thickener. Examples of the thickener include soap-based or complex soap-based thickeners, organic non-soap-based thickeners, inorganic non-soap-based thickeners, and the like. Examples of soap thickeners include lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, arachidic acid, behenic acid, zomarinic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid. Soap obtained by reacting a higher fatty acid with a base such as aluminum, barium, calcium, lithium, sodium, or potassium, and further reacting the above fatty acid with a base with acetic acid, benzoic acid, sebacic acid, azelaic acid, phosphoric acid, boric acid, or the like. Complex soap thickeners and the like.

Examples of the organic non-soap thickeners include terephthalate-type thickeners, urea-based thickeners, and fluorine-based substances such as polytetrafluoroethylene and fluorinated ethylene-propylene copolymers. However, urea thickeners are preferred. Examples of urea thickeners include, for example, monourea compounds obtained by reacting monoisocyanate and monoamine, diurea compounds obtained by reacting diisocyanate and monoamine, urea urethane compounds obtained by reacting diisocyanate, monoamine and monool, and diisocyanate. Examples include tetraurea compounds obtained by reacting a diamine and monoisocyanate.

Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, butyl isocyanate, propyl isocyanate, hexyl isocyanate, octyl isocyanate, lauryl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate phenyl isocyanate and tolylene isocyanate. Examples of the diisocyanate include hexamethylene diisocyanate and 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate,
Examples thereof include biphenyl diisocyanate and 3,3′-dimethyl biphenyl diisocyanate.

Examples of the monoamine include octylamine, nonylamine, decylamine, laurylamine,
Examples thereof include tridecylamine, myristylamine, palmitylamine, stearylamine, oleylamine, phenylamine, toluylamine, cyclohexylamine and the like. Examples of the diamine include ethylenediamine, propylenediamine, hexamethylenediamine, octamethylenediamine, phenylenediamine, diaminodiphenylmethane and the like.

Examples of monools include butanol, hexanol, 2-ethylhexanol, octanol, decanol, lauryl alcohol, tridecanol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, phenol, cresol, cyclohexanol and the like. To be

Examples of the inorganic non-soap thickener include montmorillonite, bentonite, silica aerogel, boron nitride and the like. These thickeners may be used alone or in combination of two or more. Although the amount of the thickener is not particularly limited, it is usually preferably 3 to 40% by mass, more preferably 5 to 20% by mass based on the base grease composed of the base oil and the thickener. The consistency of the base grease composed of the above base oil and thickener is not particularly limited, but is usually about 100 to 500.

The content of alkali metal in the lubricating composition of the present invention is preferably 0.02% by mass or less based on the total amount of alkali metal contained in the lubricating composition.
It is more preferable that the content is 01% by mass or less. When the alkali metal is mixed in the lubricating composition, generally, when the alkali metal is used as a catalyst, a raw material, etc. in the separation, refining, and synthesis steps of the base oil, these are not completely removed. Is mentioned. In addition, in the process of synthesizing the lubricating oil additive, an alkali metal or its salt is often used as a raw material and a catalyst, and the case where they are not completely removed can be mentioned. As the organic molybdenum compound, an inorganic substance containing an alkali metal is often used during the manufacturing process. Further, it is also possible to use sodium nitrite or sodium sulfonate as a rust preventive, or to add an alkali metal compound as a detergent dispersant.

The lubricious composition of the present invention can be used for lubrication for all purposes. For example, industrial lubricating oil,
Turbine oil, machine oil, bearing oil, compressor oil, hydraulic oil, hydraulic oil, internal combustion engine oil, refrigeration oil, gear oil, automatic transmission oil (ATF), continuously variable continuously variable transmission oil (CVTF), transformer Examples include axle fluids and metalworking oils. or,
Sliding bearings, rolling bearings, gears, universal joints, torque limiters, constant velocity joints for automobiles (CV
J), ball joints, wheel bearings, constant velocity gears, variable speed gears, and other greases.

[0058]

The present invention will be described in more detail with reference to the following examples. In the following examples,% is based on mass unless otherwise specified. First, a base oil was used as a lubricious base material, and the lubricant of the present invention was added thereto to conduct a test. The components used in the test are as follows. <Base oil> Squalene (2, 6, 10, 15, 19, 23
-Hexamethyltetraconsan) Kinematic viscosity at 100 ° C =
4.2 mm ² / sec, viscosity index (VI) = 108 <Base grease> A base grease having a consistency of 300 at 25 ° C. in which an aliphatic amine urea compound is uniformly dispersed in squalene.

<Component A: Oil-soluble molybdenum compound> (A-1) In the general formula (1), R ^{1 to} R ⁴ = 2-ethylhexyl group, and S / O of X ^{1 to} X ⁴ = 2.0 / 2. Oxymolybdenum dithiocarbamate sulfide (MoD
TC). (A-2) In the general formula (1), R ¹ = R ² = 2-ethylhexyl group, R ³ = R ⁴ = isotridecyl group, X ¹ to
MoDTC with S / O of X ⁴ = 2.0 / 2.0. (A-3) MoDTC in which R ^{1 to} R ^{4 are} isotridecyl groups and S / O of X ^{1 to} X ⁴ is 2.0 / 2.0 in the general formula (1). (A-4) In the general formula (1), R ^{1 to} R ⁴ = octadecyl group, S / O of X ^{1 to} X ⁴ is M / 2.0 = 2.0 / 2.0.
oDTC. (A-5) In the general formula (2), R ^{5 to} R ⁸ = 2-ethylhexyl group, sulfurized oxymolybdenum dithiophosphate (MoD) in which S ^{5 to} X ^{5 to} X ⁸ is S / O = 2.0 / 2.0.
TP). (A-6) In the general formula (2), R ^{5 to} R ⁸ = octadecyl group, S / O of X ^{5 to} X ⁸ is M / 2.0 = 2.0 / 2.0.
oDTP. (A-7) In the general formula (2), R ⁵ = R ⁶ = 2-ethylhexyl group, R ⁷ = R ⁸ = isotridecyl group, X ⁵ to
MoDTP with S / O of X ⁸ = 2.0 / 2.0. (A-8) A molybdenum amine salt obtained by reacting 1 mol of diisotridecylamine with molybdic acid trioxide. The isotridecyl group is a group derived from isotridecyl alcohol, which is obtained by trimerizing isobutene to synthesize dodecene by the oxo method.

<Component B: Solid lubricant> (B-1) Graphite (average particle size 2μm) (B-2) Molybdenum disulfide (average particle size 5 μm)

<C: Ashless Dispersant> (C-1) Mono-type polybutenyl succinimide (molecular weight 1000, nitrogen content 2.1% by mass) (C-2) Bis-type polybutenyl succinimide (molecular weight 1000, nitrogen content 1.7% by mass) (C-3) bis type polybutenyl succinimide (molecular weight 2000, nitrogen content 1.1% by mass) The molecular weight is GP.
It is a styrene-equivalent weight average molecular weight by C analysis.

<D: Other components> (D-1) Glycerin monooleate (D-2) Sorbitan sesquimonooleate (D-3) 2,5-dioctyl-1,3,4-thiadiazole

<Evaluation Method as Liquid Lubricating Composition> Using squalane as a base oil, liquid lubricating compositions of Examples 1 to 15 and Comparative Examples 1 to 7 were prepared with the formulations shown in Table 1 below. Using a reciprocating motion tester (HFRR tester), the coefficient of friction of these liquid lubricating compositions was measured in the point contact state of the ball-on-plate. That is, an upper ball (bearing steel ball; material φ19.05 mm, hardness about HV760) was set on a plate (bearing roller end surface mirror-finished) and reciprocally oscillated to measure a friction coefficient. The balls and plates were both SUJ-2. The detailed conditions are as follows. <Conditions> Load: 100 N Temperature: 120 ° C. Measurement time: 30 minutes Amplitude: 2.5 mm Vibration frequency: 500 cpm The friction coefficient is the average value for 10 seconds before and after the display time, for a total of 20 seconds, and is the average friction coefficient. did. For example, the average friction coefficient after 5 minutes is the average value of the friction coefficients from 4 minutes 50 seconds to 5 minutes 10 seconds. The results are shown in Table 2.

[0064]

[Table 1]

[0065]

[Table 2]

<Evaluation Method as Grease-Like Lubricating Composition> Next, the base grease prepared by dispersing the aliphatic amine urea compound in the above squalene was blended as shown in Table 3 below in Examples 16 to 30. And the grease-like lubricating compositions of Comparative Examples 8 to 14 were prepared. Using a reciprocating motion tester (HFRR tester), similar tests were conducted on these grease compositions. Table 4 shows the evaluation results.

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

The effect of the present invention is to provide a lubricating composition capable of exhibiting a sufficient friction reducing action even in the initial stage of use.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10M 125/10 C10M 125/10 129/95 129/95 133/06 133/06 133/54 133/54 133/56 133 / 56 135/18 135/18 137/10 137/10 A 159/12 159/12 // C10N 10:12 C10N 10:12 30:06 30:06 40:25 40:25 (72) Inventor Noriyoshi Tanaka 7-35, Higashiohisa, Arakawa-ku, Tokyo F-term within Asahi Denka Co., Ltd. (reference) 4H104 AA04A AA11R AA13R AA19A BC09C BE02R BF01C BF03C BG10C BH07C DA02A DB01C EB02 FA06 LA03 PA41

Claims (7)

[Claims] 1. A lubricating base material comprising an oil-soluble molybdenum compound as a component (A), a solid lubricant as a component (B),
And a lubricating composition containing an ashless dispersant as the component (C). 2. The oil-soluble molybdenum compound as the component (A) has 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 and X ⁵ to X ⁸ are as in formula (1) synonymous. ] Or a sulfided oxymolybdenum dithiophosphate represented by the following general formula (3): embedded image R ⁹ —NH—R ¹⁰ (3) (wherein R ⁹ and R ¹⁰ represent a hydrogen atom or a hydrocarbon group). Is not a hydrogen atom at the same time), and is a reaction product of an amine and a compound having a pentavalent or hexavalent molybdenum atom. 3. The solid lubricant as the component (B) is graphite and / or molybdenum disulfide.
The lubricious composition described. 4. The lubricating composition according to claim 1, wherein the ashless dispersant as the component (C) is an imide of succinic acid or a modified boric acid thereof. 5. The lubricating composition according to any one of claims 1 to 4, wherein the lubricating base material is a base oil made of mineral oil or synthetic oil. 6. The lubricating composition according to claim 1, wherein the lubricating base material is a base oil composed of squalane. 7. The lubricating composition according to claim 1, wherein the lubricating base material is a base grease made of a mineral oil or a synthetic oil and a thickener.