JP3497952B2 - Lubricating oil composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a lubricating oil composition.
In particular, it has excellent low friction properties under a wide range of sliding conditions.
And for a long time even in the presence of nitrogen oxide gas
A lubricating oil composition capable of maintaining low friction throughout
The present invention relates to a lubricating oil composition suitable as a lubricating oil for an internal combustion engine.
Things. [0002] 2. Description of the Related Art Internal combustion engines, automatic transmissions, shock absorbers, and power
The drive system equipment such as the steering should be operated smoothly.
Lubricating oil is used for this purpose. Especially for internal combustion engines
Lubricants mainly include piston rings and cylinder liners,
Bearings, cams and valves for crankshafts and connecting rods
For various sliding surfaces with different conditions, such as a valve operating mechanism including a brifter
Is required for smooth lubrication and is widely used as lubricating oil for internal combustion engines.
It is indispensable to have low friction under difficult sliding conditions
Have been. Moreover, in recent years, the fuel consumption and the output of the internal combustion engine have been reduced.
And higher operating conditions such as severer operating conditions.
Excessive lubricating oil performance has been required. Meanwhile, the internal combustion engine
Of the combustion gas in the piston and cylinder
Leakage into the crankcase as blow-by gas from between
Then, this combustion gas contains a considerably high concentration of nitrogen oxide gas.
This is the oxygen content in the blow-by gas
At the same time, it degrades the lubricating oil for internal combustion engines. In recent years
Leaks into the crankcase due to the high performance of the fuel engine
Since the concentration of nitrogen oxide gas also tends to increase,
Low friction under a wide range of sliding conditions as engine lubricant
Provides low friction coefficient over a long period of time
What you can do is extremely important. [0004] In an internal combustion engine, a friction portion in which lubricating oil is involved is used.
Large energy loss in
Conventionally, friction modifiers have been added to lubricating oil to reduce costs.
Have been. As this friction modifier, for example,
Butane compounds, fatty acid esters, alkylamines, etc.
Commonly used. Moisture using organic molybdenum compounds
As an example of a lubricating oil composition, for example, JP-A-59-122
597, and according to this publication,
(A) Oxymolybdenum sulfide organophosphorothioe
And / or molybdenum dithiocarbamate
(B) Lubricating oil composition using zinc dithiophosphate in combination
Have been. However, the lubricating oil composition obtained here
The material has a low coefficient of friction at the beginning of use, reducing friction
Although long-term use, especially nitrogen
Difficult to maintain its effect in the presence of oxide gas
The difficulty of being included. On the other hand, Japanese Patent Application Laid-Open No. H8-73878 discloses
Can maintain a low coefficient of friction over a long period of time.
It is considered that (a) molybdenum dithiocarbamate and
And (b) zinc dithiophosphate, and (c) ashless organic
An engine oil composition using a combination of polysulfides
It has been disclosed. However, this lubricating oil composition
In the region where the sliding speed is low under reciprocating friction, the friction coefficient is
There is a problem that the sliding conditions fluctuate widely
Applicable to all conditions as a lubricant for automotive internal combustion engines
Is not of sufficient quality. [0006] Therefore, the present invention provides
In view of the development situation of conventional low friction lubricating oil as described above,
Low friction in internal combustion engines even when the sliding conditions vary widely
Maintains the presence of nitrogen oxide gas over a long period of time, especially
Provides a low friction, sustainable lubricating oil composition even under
The task is to do so. [0007] Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to solve the above problems,
Molybdenum compounds and organic monosulfide compounds
A wide range of materials by combining
The coefficient of friction is low under the sliding conditions of
Found that low friction can be maintained by using
The present invention has been completed based on these findings. [0008] That is, the present invention relates to a method of adding an organic base oil to a lubricating base oil.
The molybdenum compound is defined as a molybdenum (Mo) amount of 100.
ppm to 2,000 ppm, organic monosulfide
80 ppm to 2,000 ppm as yellow (s) amount and
80 ppm of organic polysulfide as sulfur (s)
To 1,500 ppm of lubricating oil composition
Things. Further, according to a preferred embodiment of the present invention,
Mineral oil and / or synthetic oil as lubricating base oil; a) The following general formula [I] [0010] Embedded image And / or the following general formula [II] [0011] Embedded image(In the above general formulas [I] and [II], R₁ ~ R
₈ Is a hydrocarbon group, X₁ , X_Two , Y₁ And Y_Two
Is an oxygen atom or a sulfur atom. )
Molybdenum (Mo) content of 100p
pm to 2,000 ppm, b) The following general formulas [III] to [VI]                 R₉ -SR_Ten                          [III]             OHC-R₁₁-SR₁₂-CHO [IV]       R₉ OOC-R₁₁-SR₁₂-COOR_Ten            [V] [0012] Embedded image (In the above general formulas [III] to [VI], R₉ ~ R
₁₄Are hydrocarbon groups, each of which is the same or different
It may be. ) Organic monosulfide
The compound is 100 ppm to 1,800 in terms of sulfur (s).
ppm, and c) The following general formulas [VII] to [XII]                 R₁₅-Sx-R₁₆                        [VII]         R₁₅OOC-R₁₇-Sx-R₁₈-COOR₁₆        [VIII] [0013] Embedded image [0014] Embedded image OHC-R₁₇-Sx-R₁₈-CHO [XI] [0015] Embedded image (In the above general formulas [VII] to [XII], R₁₅~
R₂₀Is a hydrocarbon group, and x is an integer of 2 or more
You. Consisting of an organic polysulfide compound represented by
At least one selected from the group as sulfur (s) content
Lubricating oil set containing 100 ppm to 1,200 ppm
A composition can be provided. Hereinafter, the present invention will be described in detail. The lubricating oil used in the lubricating oil composition of the present invention
The base oil is not particularly limited.
What is used as a base oil, for example, a mineral base oil,
With any of the synthetic base oils or their mixed base oils
Can also be used. As a mineral base oil,
For example, paraffinic, intermediate or naphthenic crudes
Lubricating oil fraction obtained by vacuum distillation of atmospheric distillation residue
Solvent refining, hydrotreatment, hydrorefining, catalytic dewaxing, solvent dewaxing
Ore obtained by refining process such as wax and clay treatment
After subjecting oil and vacuum distillation residue to solvent deasphalting, remove the deasphalted oil
Mineral oil or wax obtained by processing in the refining process described above.
Mineral oil obtained by isomerization of
Mixed oils can be used. In the above solvent purification
Is phenol, furfural, N-methyl-pyrrolide
Aromatic extraction solvents, such as solvent, are used.
As the agent, propane, MEK / toluene, etc. are used.
You. On the other hand, as a synthetic base oil, for example, poly α-oleate
Fin oligomer, polybutene, alkylbenzene,
Limethylolpropane ester, pentaerythritol
Polyesters such as esters, polyoxyalkylene
Glycol, polyoxyalkylene glycol ester
, Polyoxyalkylene glycol ether, dibasic
Acid esters, phosphate esters, silicone oils, etc.
be able to. Each of these base oils can be used alone
Or two or more of them can be used in combination. Used in the lubricating oil composition of the present invention
The base oil has a viscosity of 3 mm at 100 ° C.^Two / S ~
20mm^Two / S in the range of
Ingredient (% C_A ) 3% by weight or less, sulfur content 50ppm or less
Oils and waxes with a nitrogen and nitrogen content of 50 ppm or less
Isomerized oils are particularly preferred. [0019] Friction control blended in the lubricating oil composition of the present invention
As an organic molybdenum compound as a stabilizer, for example,
The following general formula [I] [0020] Embedded image Oxymolybdenum dithiocarbamate represented by
(May be abbreviated as MoDTC), and a general formula
[II] [0021] Embedded image Oxymolybdenum sulfide organophosphorothio represented by
Eat (may be abbreviated as MoDTP)
be able to. In the above general formulas [I] and [II]
And R₁ ~ R₈ Are the same or different
And may be a hydrocarbon group having 1 to 30 carbon atoms. Charcoal
As the hydride group, a linear or branched group having 1 to 30 carbon atoms
Alkyl group; alkenyl group having 2 to 30 carbon atoms; carbon number
4 to 30 cycloalkyl groups; aryl having 6 to 30 carbon atoms
Group, alkylaryl group, arylalkyl group, etc.
Can be mentioned. In particular, an alkyl having 3 to 20 carbon atoms
Preferred is a propyl group, a butyl group, a pen
Tyl, hexyl, heptyl, octyl, nonyl
Group, decyl group, undecyl group, dodecyl group, tridecyl
Group, tetradecyl group, pentadecyl group, hexadecyl
Group, heptadecyl group, octadecyl group, etc.
A branched alkyl group can be mentioned, and in particular, has 4 to 4 carbon atoms.
Preferred are 18 alkyl groups. In addition, carbon number 4-18
Alkenyl groups can also be used. X₁ And X_Two Is
An oxygen atom or a sulfur atom;₁ And Y_Two Is oxygen
Atom or sulfur atom. Accordingly, the sulfurization represented by the above general formula [I]
As a representative example of oxymolybdenum dithiocarbamate,
Oxymolybdenum sulfide dithiocarbamate, sulfuric acid
Oxymolybdenum isopropyl dithiocarbamate,
Oxymolybdenum sulfide dithiocarbamate, sulfurized
Oxymolybdenum isobutyl dithiocarbamate, sulfurized
Oxymolybdenum pentyl dithiocarbamate, sulfurized
Ximolybdenum isopentyl dithiocarbamate, sulfurized
Oxymolybdenum hexyl dithiocarbamate, sulfurized
Ximolybdenum 2-ethylbutyl dithiocarbamate,
Oxymolybdenum sulfide heptyl dithiocarbamate, sulfuric acid
Oxymolybdenum octyl dithiocarbamate, sulfurized
Oxymolybdenum 2-ethylhexyl dithiocarbamate
G, oxymolybdenum sulfide 2-propylpentyldithio
Carbamate, oxymolybdenum nonyl dithiocarb sulfide
Bamate, oxymolybdenum sulfide 2-propylhexyl
Dithiocarbamate, oxymolybdenum decyl disulfide
Thiocarbamate, oxymolybdenum sulfide 2-methyloxide
Decyl dithiocarbamate, oxymolybdenum sulfide
Sadesil dithiocarbamate, oxymolybdenum sulfide
Kutadecyl dithiocarbamate, oxymolybdenum sulfide
2-methyloctadecyldithiocarbamate and the like
These compounds having a branched alkyl group may be mentioned.
Oxymolybdenum sulfide of the general formula [II]
Oxymolybdenum sulfide as luganophosphorothioate
Propyl phosphorodithioate, oxymolybdenum sulfide
Butyl phosphorodithioate, oxymolybdenum sulfide
Butenyl phosphorodithioate, oxymolybdenum sulfide
Pentyl phosphorodithioate, oxymolybdenum sulfide
Hexyl phosphorodithioate, oxymolybdenum sulfide
Heptyl phosphorodithioate, oxymolybdenum sulfide
Octyl phosphorodithioate, oxymolybdenum sulfide
2-ethylhexyl phosphorodithioate, oxysulfide
Molybdenum decyl phosphorodithioate, oximo sulfide
Ribendodecyl phosphorodithioate, oximo sulfide
Ribden octadecyl phosphorodithioate, oxysulfide
Or molybdenum oleyl phosphorodithioate
Having these branched alkyl or alkenyl groups
Compounds can be mentioned. Each of these compounds may be used alone.
It is possible to mix two or more
Wear. The above organic molybdenum compound has a lubricating oil composition
100 converted to molybdenum (Mo) based on the total weight of the product
ppm to 2,000 ppm, preferably 200 ppm
It is blended into the base oil at a rate of １，1,500 ppm. This distribution
If the combined amount is less than 100 ppm, a sufficient friction reducing effect cannot be obtained.
Not exceed 2,000 ppm
Not only can not obtain the effect of reducing friction
Will be caused. The organic polymer used in the lubricating oil composition of the present invention
Nosulfide compounds contain one sulfur atom in the molecule.
Has a bond that exists independently without being adjacent to the sulfur atom of
And represented by the following general formulas [III] to [VI].
Organic compounds to be used. [0027]               R₉ -SR_Ten                            [III]             OHC-R₁₁-SR₁₂-CHO [IV]       R₉ OOC-R₁₁-SR₁₂-COOR_Ten            [V] [0028] Embedded image In the above general formulas [III] to [VI], R₉ and
R_TenAre linear or cyclic hydrocarbon groups, each
May be the same or different. For example, carbon number
A linear or branched alkyl group having 1 to 20 carbon atoms;
20 straight-chain or branched alkenyl groups;
And an aryl group of 0. Preferred carbonization
Hydrogen groups are alkyl groups and aryl groups, and specific
Include methyl, ethyl, propyl, butyl,
Ethyl, hexyl, heptyl, octyl, noni
Group, decyl group, undecyl group, dodecyl group, tridecyl group
Group, tetradecyl group, pentadecyl group, hexadecyl
Group, heptadecyl group, octadecyl group, nonadecyl group,
Linear alkyl groups such as eicosyl groups and their branches
Alkyl group. But these
Without limitation, the average carbon of the two hydrocarbon groups
If the number is in the range of 1 to 20, two hydrocarbon groups
One hydrocarbon group may be a longer-chain alkyl group
Can also be used. Further, as the aryl group,
Phenyl, tolyl, xylyl, biphenyl,
And an aryl group having a carbon number.
It may be one having 1 to 14 alkyl groups bonded thereto. S
Specific examples of the alkylating group include methyl oleate.
Methyl group, methyl stearate group, triglyceride oleate
Group, methyl ester group of vegetable oil, glycerin of vegetable oil
Ester group, glycerin ester group of animal oil,
R> methyl ester group and the like can be used. R₁₁And R₁₂Is a chain or cyclic hydrocarbon
And may be the same or different
And a hydrocarbon group having two binding sites. In particular, charcoal
An alkyl group having a prime number of 1 to 18 is preferred. R₁₃And R₁₄
Is a chain hydrocarbon group, preferably an alkyl group similar to the above.
Good. Therefore, organic monosulfide compounds are preferred.
Preferred specific examples are dialkyl monosulfide,
For example, dimethyl monosulfide, diethyl monosulfide
Fido, di-n-propyl monosulfide, di-n
-Butyl monosulfide, di-n-pentyl monosul
Fido, di-n-hexyl monosulfide, di-n
-Cetyl monosulfide, di-n-octyl monosulfate
Fido, di-n-nonyl monosulfide, di-n-
Decyl monosulfide, di-n-tridecyl monosul
Sulfide, di-n-hexadecyl monosulfide, di
-In addition to n-octadecyl monosulfide,
Monosulphide, for example diphenyl monosulphate
Fluoride, dibenzyl monosulfide,
Cyl monosulfide, methyl monostearate
Fido, di (trioleic acid glyceride) monosulfate
And those having a branched alkyl group
Sulfide and the like can be mentioned. The amount of the organic monosulfide compound is as follows:
80 ppm to 1,800 pp in terms of sulfur (s)
m, preferably from 100 ppm to 1,500 ppm
You. 80 ppm of organic monosulfide compound
If the sliding speed is not reached,
The effect on reducing the coefficient of friction is not sufficient, and
Even if it exceeds 000 ppm, the friction reduction effect corresponding to the increase
Not only do not appear, but also the occurrence of corrosion becomes severe,
Problem arises. The organic resin used in the lubricating oil composition of the present invention
Resulfide compounds have two or more sulfur atoms in the molecule.
Is an organic compound having an adjacent bond,
[VII] to [XII]                 R₁₅-Sx-R₁₆                        [VII]         R₁₅OOC-R₁₇-Sx-R₁₈-COOR₁₆        [VIII] [0033] Embedded image [0034] Embedded image OHC-R₁₇-Sx-R₁₈-CHO [XI] [0035] Embedded image Is represented by The above general formulas [VII] to [XII]
IAnd R₁₅And R₁₆Is a chain or cyclic hydrocarbon group
And may be the same or different from each other,
An aliphatic hydrocarbon group or an aromatic hydrocarbon group of Formulas 1 to 20
Can be mentioned. Particularly, alkyl group, alkenyl
Groups, aryl groups, esterified alkyl groups and the like are preferred.
As the alkyl group, specifically, methyl group, ethyl
Group, propyl group, butyl group, pentyl group, hexyl group,
Heptyl, octyl, nonyl, decyl, unde
A sil group, a dodecyl group, a tridecyl group, a tetradecyl group,
Pentadecyl, hexadecyl, heptadecyl,
Straight chain such as kutadecyl, nonadecyl, eicosyl, etc.
An alkyl group or a branched alkyl group thereof. I
However, the present invention is not limited to these.
Alkyl groups can also be used. In addition, an aryl group and
Phenyl, tolyl, xylyl, biphenyl
And a naphthyl group.
An alkyl group having 1 to 14 carbon atoms bonded to the
May be. As the esterified alkyl group, specifically,
Are methyl oleate, methyl stearate,
Inic acid triglyceride group, methyl ester group of vegetable oil,
Glycerin ester group of vegetable oil, glycerin ester of animal oil
Use of steal groups, methyl ester groups of animal oil, etc.
it can. R₁₇And R₁₈Is a chain or cyclic hydrocarbon group
And may be the same or different from each other,
It is a hydrocarbon group having two sites. In particular, carbon number 1
18 alkylene groups are preferred. R₁₉And R₂₀Is a chain
Hydrocarbon group, preferably the same alkyl group as described above.
No. In the above general formulas [VII] to [XII], x is
It is an integer of 2 or more, preferably about 2 to 6. Accordingly, preferred organic polysulfides
Specifically, specifically, dialkyl disulfide, dia
Lucyl trisulfide and other dialkyl polysulfates
, Diphenyl disulfide, diphenyl trisa
Sulfide, other diphenyl polysulfide, gibe
Nyl disulfide, polyolefin polysulfide
, Bisalkyl polysulfanyl thiadiazole, sulfuric acid
Olefins, sulfide fish oil, sulfide whale oil, sulfide pinene, etc.
I can do it. In particular, dialkyl disulfides,
Diphenyl disulfide, bisalkyl polysulfur
Nilthiadiazole and the like are preferred. Dialkyl disulf
For example, dimethyl disulfide, di
Ethyl disulfide, di-n-propyl disulfide
, Di-n-butyl disulfide, di-n-pentyl
Disulfide, di-n-hexyl disulfide, di
-N-cetyl disulphide, di-n-octyl disul
Fide, di-n-nonyl disulfide, di-n-de
Sildisulphide, di-n-tridecyldisulfide
, Di-n-hexadecyl disulfide, di-n-o
Kutadecyl disulphide, methyl disoleate
Fide, methyl distearate disulfide, di
(Trioleic acid glyceride)
For example, diaryl disulfides such as diphenyl disulfide
Sulfide, dibenzyl disulfide and the like
And disulfides having a branched alkyl group.
Can be The amount of the organic polysulfide compound is as follows:
80 ppm to 1,500 ppm in terms of sulfur (s)
And preferably at 100 ppm to 1,200 ppm
is there. If the compounding amount is less than 80 ppm, friction reduction is reduced.
Effect is insufficient, while exceeding 1,500 ppm
In this case, corrosion wear may increase. Further, an organic monosulfide compound and
The total sulfur content from the organic polysulfide compound is 16
0 ppm to 3,500 ppm, preferably 20 ppm
It is 0 ppm to 2,500 ppm. The lubricating oil composition of the present invention may contain an antiwear agent.
Represented by the following general formulas [XIII] and [XIV]
Zinc dithiophosphate (ZnDTP) and dithiocarba
Zinc formate (ZnDTC) can be used. [0041] Embedded image [0042] Embedded image In the above general formulas [XIII] and [XIV], R
_{twenty one}~ R_{twenty four}Is a hydrogen atom or a hydrocarbon having 1 to 26 carbon atoms
And the hydrocarbon group is a first group having 1 to 26 carbon atoms.
Grade (primary) or secondary (secondary) al
Kill group; alkenyl group having 2 to 26 carbon atoms; 6 to 2 carbon atoms
A cycloalkyl group having 6; an aryl group having 6 to 26 carbon atoms;
An alkylaryl group or an arylalkyl group; or
Ester bond, ether bond, alcohol group or cal
It is a hydrocarbon group containing a boxyl group. R_{twenty one}~ R_{twenty four}Is good
Preferably, it is an alkyl group having 2 to 12 carbon atoms, and 8 to 18 carbon atoms.
A cycloalkyl group, an alkyl aryl having 8 to 18 carbon atoms
Each of which is the same or different
Is also good. ZnDTP and ZnDTC are each simply
Can be used alone or in combination
And its use ratio is 0.1% based on the total weight of the lubricating oil composition.
% To 7% by weight, preferably 1% to 5% by weight
is there. The lubricating oil composition of the present invention further comprises
As long as the purpose of the light is not impaired,
Additives, such as other friction modifiers,
Cleaning agents, other abrasives, ashless dispersants, antioxidants, viscosity index
Improvers, pour point depressants, defoamers, rust inhibitors, corrosion inhibitors, etc.
Can be appropriately compounded. Other friction modifiers include, for example, polyvalent
Alcohol partial esters, amines, amides, sulfurized esters
And the like. As the metal-based detergent, for example, calcium
Musulfonate, calcium phenate, calcium salt
Resilate, magnesium sulfonate, magnesium
Phenate, magnesium salicylate, etc.
You. These are usually used in a proportion of 0.05 to 5% by weight.
You. Other antiwear agents include, for example, phosphoric acid
Steal, phosphite and the like.
Are usually used at a ratio of 0.05 to 5% by weight. Examples of the ashless dispersant include succinic acid
Amide, succinamide, benzylamine, esthetic
And the like, and even boronized ones
Good. These are usually used in a proportion of 0.5 to 7% by weight.
It is. As the antioxidant, for example, alkylated
Diphenylamine, phenyl-α-naphthylamine,
Alkylation-Prevention of amine-based oxidation such as α-naphthylamine
Agent, 2,6-di-t-butyl-4-methylphenyl,
4,4'-methylenebis (2,6-di-t-butylphenyl
Phenolic antioxidants such as
It is usually used in a proportion of 0.05 to 4% by weight. As the viscosity index improver, for example, polymer
Tacrylate, polyisobutylene, ethylene-pro
Pyrene copolymer, hydrogenated styrene-butadiene copolymer
And the like, which are usually 0.5 to 35% by weight.
Used in proportions. Examples of pour point depressants include polyal
Killed methacrylate, chlorinated paraffin-naphthalene
And alkylated polystyrene. As an antifoaming agent, for example, dimethylpolyester
Loxane and polyacrylic acid. As rust preventives, for example, fatty acids, alk
Nylsuccinic acid partial ester, fatty acid soap, alkyl
Sulfonates, fatty acid polyhydric alcohol esters, fatty acids
Amine, paraffin oxide, alkyl polyoxyethylene
Ether and the like. As the corrosion inhibitor, for example, benzotri
Azole, benzimidazole and the like can be mentioned. [0055] DETAILED DESCRIPTION OF THE INVENTION Mineral oil (kinematic viscosity 3 mm^Two / S ~ 20
mm^Two / S @ 100 ° C) as the lubricating base oil
Molybdenum-N, N-di (2-ethylhexyl) dithio
Molybdenum (Mo) content is 300pp
m ~ 1,500ppm, diphenyl monosulfide
300 ppm to 1,800 ppm of sulfur (s)
And diphenyl disulfide as sulfur (s)
00ppm-1,000ppm, furthermore, wear prevention
Stopper, metal detergent, ashless dispersant, antioxidant, viscosity index
Lubricating oil composition containing effective amount of improver and pour point depressant
Things are provided. [0056] EXAMPLES The present invention will be further described with reference to Examples and Comparative Examples.
This will be described in detail. As a lubricating base oil, 150 neutral oils
(5.3mm^Two / S @ 100 ° C) as an additive
The following were used: 1) Organic molybdenum compounds C₈ MoDTC: oxymolybdenum sulfide-N, N-di
(2'-ethylhexyl) dithiocarbamate C₈ MoDTP: oxymolybdenum sulfide (2-ethyl
Hexyl) phosphorodithioate 2) Organic monosulfide compounds C₈ MS: di-n-octyl monosulfide DPMS: diphenyl monosulfide 3) Organic polysulfide compound C₈ DS: di-n-octyl disulfide DPDS: diphenyl disulfide Additives were added to the above base oils at the ratios shown in Tables 1 and 2.
A lubricating oil composition was prepared. To the resulting lubricating oil composition
Characteristics of new oil and used oil after NOx oxidation test
Was evaluated by the following measurement method. 1) Friction property evaluation method Reciprocating friction test shown in Fig. 1 for new and used oils
Characteristics under a wide range of friction conditions
Therefore, the friction coefficient was measured under the following test conditions. The coefficient of friction is
The value after a test time of 20 minutes was used. In the friction test, as shown in FIG.
An oil film is formed on the disc, and the cylinder is placed on top of it.
Apply a specified load and shake the cylinder horizontally for a specified width.
I let you. Material is DIN100C for both cylinder and disk
R₆ (HRc62, JISSUJ2 equivalent) was used.Test condition Condition 1 Condition 2               Load, N 400 400     Oil temperature, ℃ 80 80     Frequency, Hz 50 50     Amplitude, mm 0.5 2.0     (Average sliding speed m / s) (0.025) (0.1)     Hours, minutes 20 20 The oil used was obtained after the NOx oxidation test under the following conditions.
It was subjected to the friction test described above in the same manner as the new oil.
The rubbing properties were evaluated.NOx oxidation test conditions Oil temperature, ℃ 150 Processing time, h5 Nitrogen oxide gas, NO_Two Concentration vol% 1 Gas flow rate, l / h 3 Examples 1 to 10 Examples 1 to 10 show that, as shown in Table 1,
The present invention relates to a friction lubricating oil composition. Examples 1 to 3 use 150 neutral oils.
C as base oil and organic molybdenum compound₈ MoDTC
(Oxymolybdenum sulfide-N, N-di (2-ethylhexyl)
Syl) dithiocarbamate) and organic monosulfur
Obtained by using a combination of a sulfide compound and an organic polysulfide compound.
1 shows an obtained low friction lubricating oil composition. Examples 4 to 6 show that the organic molybdenum compound
And C in Examples 1 to 3₈ Instead of MoDTC, C₈ M
oDTP (oxymolybdenum sulfide (2-ethylhexyl)
F) phosphorothioate), using organic monosulfide
Combined with a polysulfide compound and an organic polysulfide compound
1 presents a friction lubricating oil composition. Further, in Examples 7-10, the organic molybdenum
The above-mentioned C₈ MoDTC and C₈ MoDT
P together with an organic monosulfide compound
Friction Lubricating Oil Combination Combined with Combination Polysulfide Compound
It shows a product. Comparative Examples 1 to 9 In Comparative Examples 1 to 6, as shown in Table 2, the organic molybdenum
Compound alone or organic molybdenum compound and organic monosulfate
Using a sulfide compound and an organic polysulfide compound
But the amount of the lubricating oil composition is out of the range of the present invention.
It is something. Comparative Example 1 was an organic molybdenum compound.
C₈ Organic monosulfide using only MoDTC
Compounds and organic polysulfide compounds
A lubricating oil composition in which no lubricant was used.
The same amount of C as compared to the oil composition₈ Contains MoDTC
However, since it does not contain the above sulfur compounds,
The coefficient of friction is high for both oil and used oil.
The coefficient results have been shown to be particularly high. Comparative Example 2
Represents C as an organic monosulfide compound₈ MS, Yes
C as a polysulfide compound₈ Yes with DS
But C₈ The compounding amount of MS is 50 pp as sulfur (s) amount.
m and the range of the compounding amount of the organic monosulfide compound of the present invention.
Indicate the lubricating oil composition outside the box,
Sulfide compound and organic polysulfide compound
The amount of organic monosulfide compound
If the amount is less than the specified value, the friction coefficient of Condition 1 may increase.
It is shown. On the other hand, from Comparative Example 3, the organic polysulfur
If the amount of the compound is less than the specified amount, the friction of condition 2
A higher coefficient is observed. Comparative Example 4 is C₈ M
C instead of oDTC₈ Uses MoDTP
The lubricating oil composition lacks the specified amount of DPDS of 40 ppm
And the coefficient of friction under Condition 2 is extremely high. Comparative Example 5
6 shows that the compounding amount of the organic molybdenum compound satisfies a predetermined amount.
Shows no lubricating oil composition, new oil, used oil
The result is a remarkably high co-friction coefficient. In Comparative Examples 7 and 8, the organic molybdenum compound was used.
The thing is C₈ MoDTC was blended in the same amount as in Example 1.
But the organic monosulfide compound (C₈ MS) only
Used without organic polysulfide compound
1 shows a lubricating oil composition. In Comparative Example 8, an organic polysulfide compound was used.
(C₈ DS) only, organic monosulfide compound
This is an example of a lubricating oil composition that was not used in combination.
All have a high coefficient of friction.
Monosulfide Compounds and Organic Polysulfide Compounds
It is understood that the combination of objects is essential. On the other hand, according to Comparative Example 9, the organic monosulfur
Compound (C₈ MS) and organic polysulfide compound
Object (C₈ DS), but with an organic molybdenum compound
This is an example of a lubricating oil composition lacking a material, and
Unless a lithium compound is used, a sufficient friction reduction effect can be obtained.
It is clear that not. [0065] [Table 1][0066] [Table 2][0067] The present invention relates to an organic molybdenum compound,
Monosulfide compounds and organic polysulfides
And the essential components, each containing a specific amount
Provides lubricating oil composition with different sliding speed
Excellent low friction under a wide range of sliding conditions
Both have oxidation resistance even in the presence of nitrogen oxide gas.
It is possible to maintain low friction by applying. Therefore, the present invention
The lubricating oil composition is used for internal combustion engines, automatic transmissions, shock absorbers,
-Suitable as lubricating oil for internal combustion engines, especially for steering
is there.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a basic conceptual diagram of a friction tester used for measuring a friction coefficient of a lubricating oil composition of the present invention. [Explanation of symbols] 1 cylinder 2 disc

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI (C10M 141/10 C10N 10:12 135: 20 30:06 137: 10) 30:10 C10N 10:12 40:25 30:06 30:10 40:25 (58) Field surveyed (Int.Cl. ⁷ , DB name) C10M 135/00-135/36 C10M 137/10 C10M 141/10 C10N 10:12 C10N 30:06 C10N 30:10 C10N 40:25-40:28

Claims (1)

(57) [Claims 1] An organic molybdenum compound is added to a lubricating base oil in an amount of 100 ppm to 2,000 as a molybdenum (Mo) amount.
ppm, the following general formulas [III] to [VI] R ₉ -SR ₁₀ [III] OHC-R ₁₁ -SR ₁₂ -CHO [IV] R _{9 OOC-R 11 -S-R 12} -COOR 10 [V] [Formula 1] (In the above general formulas [III] to [VI], R ₉ ~ R
₁₄ is a hydrocarbon group, each of which is the same or different
It may be. ) Is 80 ppm to 2,000 p as sulfur ( S ) amount.
pm, and the organic polysulfide compound is sulfur ( S )
A lubricating oil composition containing 80 ppm to 1,500 ppm as an amount.