JP2001200282A - Lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorus-containing lubricant hardly corroding a metal and excellent in extreme pressure properties. SOLUTION: The lubricant composition comprises a lubricant base material and, incorporated therein, a component (A): an organic molybdenum compound and a component (B): a compound represented by general formula (B) (wherein Ra, Rb and Rc are each a hydrocarbyl group; m is a number of 0 or at least 1; k is a number of at least 1; n is a number of 1-2; and p is 0 or 1). Preferably, the organic molybdenum compound is molybdenum oxysulfide thiocarbamate, molybdenum oxysulfide thiophosphate or a reaction product of an amine with a molybdenum compound.

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 promoting fuel efficiency in automobiles,
Improvement of the engine oil is also an important factor, such as reducing the weight of the vehicle itself, improving the engine, improving the vehicle itself, lowering the viscosity of the engine oil to prevent friction loss in the engine, and adding a good friction modifier. Has become. 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 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 abrasion due to the reduction in viscosity have newly occurred. Engine oil also plays an important role in lubrication of valve trains, bearings, etc., but mixed lubrication and boundary lubrication are common in this part, so lowering 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 are added to various lubricating oils because they have an excellent friction reducing effect. In particular, in the case of engine oils, the frictional resistance of each part of the engine is reduced, and the result is reduced. It is effective in reducing fuel consumption, that is, so-called fuel saving, and has become an indispensable additive for fuel saving oil. 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, even if the lubricating oil deteriorates due to long-term use, it is an important theme required for the current fuel-saving oil to maintain a certain level of friction reducing action.

[0004]

As described above, organic molybdenum compounds are indispensable additives for high-performance lubricating oils such as fuel-saving oils. Naturally, organic molybdenum compounds are used as additives. The desired performance cannot be exhibited only by containing. Therefore, an additive to be used in combination with the organic molybdenum compound is required. For example, extreme pressure agents are additives that exhibit wear resistance under severe conditions. Typical extreme pressure agents are sulfur-based, chlorine-based, phosphorus-based and the like.
However, chlorine-based extreme pressure agents are excellent in abrasion resistance,
In addition to problems such as skin rash and rust, the amount used is decreasing due to dioxin problems.
Sulfur compounds are also excellent in lubricity and extreme pressure,
There are many problems because many have a unique odor.

[0005] Phosphorus extreme pressure agents have been considered as alternatives to chlorine extreme pressure agents. Examples of the phosphorus-based additive include a phosphoric acid ester (salt) type, a phosphite ester (salt) type, a thiophosphoric acid ester (salt) type, and a phosphine type. For example, JP-A-6-192676 discloses a plastic working oil composition containing an acidic phosphate ester amine salt such as lauryl acid phosphate cocoalkylamine salt in a lubricating base oil. Also, JP-A-8-134488
The publication discloses a lubricating oil composition containing, in a base oil, an acidic phosphate ester amine salt such as a salt of octyl acidic phosphate ester and diisotridecylamine, and a linear alkylamine.

However, these acidic phosphate ester lubricants have a problem that they are corrosive to metals. In order to solve this, conventionally, it has been used after neutralization with an alkali such as sodium hydroxide or an amine such as an alkylamine or an alkylalkanolamine. However, in some cases, neutralization with amines was sometimes insufficient, and corrosion occurred to metals.

The inventors of the present invention have studied diligently, and have developed a phosphorus-based lubricant which is hardly corroded to metals and has good extreme pressure properties by modifying an acidic phosphate with an alkylene oxide. By using in combination with an organic molybdenum compound, an excellent lubricating composition has been developed.

[0008]

That is, the present invention provides a lubricating base material comprising an organic molybdenum compound as the component (A) and a compound represented by the following general formula (B) as the component (B):

[0009]

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(Wherein, R ^a , R ^b and R ^c represent a hydrocarbon group, m represents 0 or a number of 1 or more, k represents a number of 1 or more, and n represents a number of 1 to 2) And p represents 0 or 1.).

Further, the present invention provides a lubricating base material having the following general formula (4) as a component (C) in addition to the components (A) and (B).

[0012]

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(Wherein, R ¹¹ and R ¹² represent a hydrocarbon group, and a represents a number of 0 to 1/3). This is a lubricating composition containing zinc dithiophosphate.

Further, the present invention provides a method for producing a lubricating base material, comprising:
In addition to the components (B) and (C), the following (D)
1) to (D13) components (D1) Metal detergent (D2) Ashless dispersant (D3) Compound containing phosphorus atom (D4) Compound containing phosphorus atom and sulfur atom (D5) Metal containing sulfur atom Compound containing no atom (D6) Antioxidant (D7) Organometallic compound (D8) Oiliness improver containing no metal, phosphorus and sulfur atoms (D9) Rust inhibitor (D10) Viscosity index improver (D11) Metal deactivator (D12) Antifoaming agent (D13) A lubricating composition containing one or more of solid lubricants.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The component (A) of the present invention is an organic molybdenum compound. As the organic molybdenum compound,
For example, fatty acid molybdenum salt, 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, succinimide Carboxylic acid amide or Mannich base or a reaction product of a boride thereof with molybdenum trioxide. The most preferred organic molybdenum compound is oxymolybdenum dithiocarbamate sulfide represented by the following general formula (1). Or a molybdenum amine reactant which is a reaction product of a sulfurized oxymolybdenum dithiophosphate represented by the following general formula (2) or a compound having a pentavalent or hexavalent molybdenum atom represented by the following general formula (3).

[0016]

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

[0018]

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(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 cannot be a hydrogen atom at the same time.)

In the above general formulas (1) to (3), R
^{1 to} R ⁸ are a hydrocarbon group, and R ^{9 to} R ¹⁰ are a hydrogen atom or a hydrocarbon group. Examples of these hydrocarbon groups include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.

Examples of the alkyl group include 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 group and the like.

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

R ⁹ and R ¹⁰ may be hydrogen atoms,
They cannot be hydrogen atoms at the same time. R ^{1 to} R ¹⁰ may be the same or different from each other. That is, R ^{1 to} R ⁴ , R ^{5 to} R ⁸ ,
R ^{9 to} R ¹⁰ may be the same or different from each other. R ^{1 to} R
^{In the} case where ⁴ is different from each other, it is preferable in order to lengthen the drainage of the lubricating oil composition (extend the service life).

Among them, 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, an alkyl group having 8 to 13 carbon atoms in sulfided oxymolybdenum dithiocarbamate, and R ^{5 to} R ⁸ , that is, an alkyl group having 6 to 13 carbon atoms in sulfided oxymolybdenum dithiophosphate. The alkyl group having 13 carbon atoms, R ^{9 to} R ¹⁰ , that is, the alkyl group having 6 to 18 carbon atoms is preferable for the molybdenum amine reactant. this is,
If the carbon number of the group represented by R ^{1 to} R ¹⁰ is too small, the oil solubility becomes poor. If the carbon number is too large, the melting point becomes high, the handling becomes poor, and the 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 and 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 3 in number ratio. / 1 is particularly preferred.

As the pentavalent or hexavalent molybdenum compound to be reacted with the amine represented by the general formula (3), 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 represented by the above general formula (1) can be used.
One of a sulfurized oxymolybdenum dithiophosphate represented by the general formula (2) or a molybdenum amine reactant which is a reaction product of the amine represented by the general formula (3) and a compound having a pentavalent or hexavalent molybdenum atom Use of only one kind or two or more kinds may be used in combination. When two or more kinds are used in combination, it is preferable to use at least one kind of oxymolybdenum dithiocarbamate 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 friction reducing effect 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 (approximately 0.03% by weight or less in terms of the amount of molybdenum relative to the lubricating base material), the anti-wear effect is obtained. It is said that the reduction effect appears remarkably. Therefore, the amount of addition is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, still more preferably 0.01 to 1% by weight in terms of molybdenum relative to the lubricating substrate.

The component (B) of the present invention has the general formula (B)
(Hereinafter, these are collectively referred to as “(phosphite) phosphate ester)”. In the general formula (B), Ra represents ^a hydrocarbon group. Examples of the hydrocarbon group include the same groups as R ^{1 to} R ¹⁰ . The group preferable as ^Ra is preferably an alkyl group or an alkenyl group from the viewpoints of load resistance, anti-seizure property and odor of the product, and has 6 to 6 carbon atoms.
More preferably, it is 22 alkyl groups or alkenyl groups.

In the general formula (B), R^bAnd R^cIs
Represents a hydrocarbon group, but is an alkylene group having 2 to 4 carbon atoms.
Preferably, there is. (R) of the general formula (B)^b-O)_mOr
(R ^c-O)_kIs ethylene oxide, propylene
Oxide, butylene oxide, tetrahydrofura
(1,4-butylene oxide), long-chain α-olefin
Alkylene oxides such as oxides and styrene oxides
It can be obtained by addition polymerization of the side and the like.
By adding an alkylene oxide or the like, (R^b
-O)_mOr (R^c-O)_kWhen forming the part of
Depending on the kind of alkylene oxide to be added, R^bas well as
R^cIs determined. Alkylene oxide to be added
The polymerization form of is not particularly limited, and one type of alkylene oxide
Homopolymerization of side, etc., two or more alkylene oxides
Random copolymerization, block copolymerization or random /
It may be a block copolymer or the like. R^bAnd R^cAs d
Tylene or propylene groups are most preferred;^bAnd R^c
If is more than one group, one must be an ethylene group
Is preferred. m represents 0 or a number greater than or equal to 1, and k represents 1
The above numbers are represented, and n represents a number of 1 to 2.

In the general formula (B), p represents 0 or 1. That is, when p is 0, the compound represented by the general formula (B) is a phosphite derivative, and when p is 1, the compound represented by the general formula (B) is a phosphate ester derivative. The compound represented by the general formula (B) is usually produced and used as a mixture of a monoester where n = 1 and a diester where n = 2. The mixing ratio of the monoester and the diester can be appropriately selected depending on the raw material ratio at the time of production and the amount of water added in the process.
These (phosphite) phosphoric acid esters may contain a pyro-type compound or a poly-type compound generated during the production process.

The method for producing the compound represented by the general formula (B) includes the steps of reacting an alcohol having a group represented by R ¹ -OH or a compound obtained by adding an alkylene oxide to this alcohol with a phosphoric acid esterifying agent or phosphorous acid. After phosphoric acid esterification or phosphite esterification by a known method using an acid esterifying agent, the remaining hydroxyl groups may be further reacted with an alkylene oxide. Examples of the phosphate esterifying agent include diphosphorus pentoxide, orthophosphoric acid, polyphosphoric acid, and the like. Examples of the phosphite esterifying agent include phosphorous acid and the like. The compound represented by the general formula (B) is a compound represented by the following formula:
Since it is inactivated by adding an alkylene oxide or the like, there is almost no corrosion to the metal.

The lubricating composition of the present invention may further contain (C) a component, if necessary. The component (C) of the present invention is zinc dithiophosphate represented by the general formula (4). (C) The lubricating composition of the present invention
By blending the components, the oxidation stability and the long drain property are further improved. In the general formula (4), R ¹¹ and R ¹² are a hydrocarbon group. 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. 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 component (C) is not particularly limited, but it is preferable to add a certain amount in order to exert a practical friction reducing effect and an antioxidant effect. In some cases, the amount of phosphorus is preferably 0.001 to 3% by weight, more preferably 0.005% by weight, based on the lubricating base material.
To 2% by weight, more preferably 0.01 to 1% by weight.

The lubricating composition of the present invention further contains (D1) a metal detergent, (D2) an ashless dispersant, and (D3) a phosphorus atom, depending on the purpose of use. Compound, (D4) Compound containing phosphorus atom and sulfur atom, (D5) Compound containing sulfur atom and not containing metal atom, (D6) Antioxidant, (D7) Organometallic compound, (D8) Metal atom , An oiliness improver containing no phosphorus and sulfur atoms, (D9) a rust preventive, (D10) a viscosity index improver, (D11) a metal deactivator, (D12) a defoamer, and (D13) a solid lubricant Etc. 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,
Barium is more preferred. 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 200-500 m
It is about gKOH / g.

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 weight. 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) (however, excluding arrows)

[0041]

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(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)

[0043]

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(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. As benzylamine (Mannich reaction product), for example, a compound represented by the following formula (D2-3) (excluding arrows)

[0045]

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(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)

[0047]

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(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 general formula (D2-5) (However, except for arrows)

[0049]

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(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 group is usually about 300 to 4,000.

The boron-modified products of the above compounds include:
For example, the following substituent (D2
-A)

[0052]

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Or the following general formula (D2-b)

[0054]

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And the like are coordinated. The nitrogen content in the ashless dispersant is usually 0.5 to 2.0% by weight.
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 weight.

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.

The alkylidenebisphosphine represented by (R) ₂ P— (CH ₂ ) _n —P (R) ₂ includes, for example, methylenebis (dibutylphosphine), methylenebis (dihexylphosphine), methylenebis (dioctylphosphine), methylenebis (Di-2-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 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.

Examples of the organic phosphite represented by (RO) ₃ P include, for example, monobutyl phosphite, dibutyl phosphite, and tributyl phosphite (hereinafter, referred to as tributyl phosphite).
These are collectively abbreviated as "mono / di / tributyl 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 / di / trimyristyl phosphite, mono / di / tripalmityl phosphite, mono / di / tristearyl phosphite, mono / di / trioleyl phosphite, mono / di / Triphenyl phosphite, mono / di /
And tricresyl phosphite. Examples of other phosphites include pentaerythritol diphosphite, pentaerythritol tetraphosphite, and alkylidenebisphosphite.

Examples of the organic phosphate represented by (RO) ₃ PＯO include mono / di / tributyl phosphate, mono / di / trihexyl phosphate, and mono / di / trihexyl phosphate.
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 / tri Examples include stearyl 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 phosphates, 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. Examples of the amine include ammonia; methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, butylamine, hexylamine, octylamine,
Alkylamines such as decylamine, dodecylamine, tridecylamine, cetylamine, cocoalkylamine, alkylamine derived from soybean oil, alkylamine derived from tallow, oleylamine and stearylamine; monoethanolamine, N-methylmonoethanolamine, N-ethyl Monoethanolamine, 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)
Alkanolamines such as ethylenediamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or alkylene oxide adduct thereof; N-butyldiethanolamine, N-hexyldiethanolamine, N-octyldiethanolamine;
N-decyldiethanolamine, N-cocoalkyldiethanolamine, N-soybean oil-derived alkyldiethanolamine, N-tallow-derived alkyldiethanolamine, N
Oleyldiethanolamine, N-stearyldiethanolamine, N, N-dibutylmonoethanolamine, N, N-dihexylmonoethanolamine, N, N
-Dioctylmonoethanolamine, N, N-didecylmonoethanolamine, 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-distearyl monoethanolamine, etc. N-long-chain alkyl alkanolamines or alkylene oxide adducts thereof are exemplified. Examples of the phosphoramidate include those obtained by subjecting the above-mentioned phosphate and the above-mentioned amine to a condensation reaction. (D
3) The preferable compounding amount of the component is 0.1 to the lubricating base material.
It is about 1 to 5% by weight.

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, mono / di / tributyltrithiophosphite, mono / di / trihexyltrithiophosphite, mono / di / trioctyltrithiophosphite, and mono / di / trioctyltrithiophosphite. / Di / tri (2-ethylhexyl) trithiophosphite, mono / di / trinonyltrithiophosphite, 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 / triphenyl trithiophosphite, mono / di / tricresyl trithiophosphite and the like. Can be

Examples of the organic thiophosphate represented by (RO) ₃ P = S include mono / di / tributyl thiophosphate, mono / di / trihexyl thiophosphate, mono / di / trioctyl thiophosphate, and 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. Further, dithiophosphoric acid dimers can also be used. The preferred amount of the component (D4) is about 0.1 to 5% by weight based on the lubricating base material.

Compounds containing a sulfur atom as a component (D5) and not containing a metal atom include, for example, 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- _Sx- R (D5-1) (wherein, R represents a hydrocarbon group which may have a substituent).

Examples of such organic mono- or polysulfides include dimethyl mono / di / polysulfide, diethyl mono / di / polysulfide, dipropyl mono / di / polysulfide, diisopropyl mono / di / polysulfide, dibutyl mono / di / polysulfide, diisobutyl monosulfide. / 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, disulfide Isostearyl 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, 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 (butylphenyl) 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 / 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,
Di (ethylhydroxy) dihydrocarbyl sulfide such as dicyclohexyl mono / di / polysulfide, dicycloheptyl mono / di / polysulfide, dimethylcyclopentyl mono / di / polysulfide, dimethylcyclohexyl mono / di / polysulfide, dimethylcycloheptyl mono / di / polysulfide, etc. Phenyl)
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 / polysulfide, di (undecylhydroxyphenyl) mono / Ji /
Polysulfide, di (dodecylhydroxyphenyl)
And dihydrocarbylphenol sulfides such as mono / di / polysulfide. The 1,3,4-thiadiazole derivative has the following general formula (D5-2)

[0068]

Embedded image

(In the formula, R represents a hydrocarbon group or a hydrocarbon group containing a sulfur atom.)

The sulfur-containing hydrocarbon groups include:
For example, 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,
Examples thereof include octyldithio, stearylthio, laurylthio, octylthio, and N, N-dialkyldithiocarbamoyl. Among them, a group in which two to four sulfur atoms are continuously bonded is particularly preferable. Thiuram disulfide is
The following general formula (D5-3)

[0071]

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)

[0073]

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 weight.

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 abbreviated as t-butyl), 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-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'-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, and laurylstearylthiopionate. Dipropionate, 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 '- thiodi (3-methyl -5-t
-Butyl-4-phenol) ester, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, amylthioglycolate and the like. The preferable blending amount of the component (D6) is about 0.01 to 5% by weight based on the lubricating base material.

The organometallic compound (D7) improves wear 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, fatty acids such as linolenic acid or lithium of naphthenic acid ,
Examples thereof include sodium, potassium, magnesium, calcium, barium, titanium, zinc, lead, tin, iron, cadmium, cobalt, nickel, manganese, strontium, vanadium, copper, antimony, bismuth, and tungsten salts. The fatty acid preferably has about 12 to 18 carbon atoms. Further, a metal salt of dithiophosphate, a metal salt of dithiocarbamic acid, a metal salt of mercaptobenzothiazole, a metal salt of mercaptobenzimidazole, a metal salt of benzamidothiophenol and the like can be mentioned. The metal atom is the metal atom exemplified above.

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, behenylamine; 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 mono / di / triglyceride, decanoic mono / di / triglyceride, lauric mono / di / triglyceride, myristic mono / di / triglyceride, palmitic mono / di / triglyceride, mono / di / stearic acid Glycerides such as triglyceride, oleic acid mono / di / triglyceride, behenic acid mono / di / triglyceride, etc .; polyglycerin hexanoate, polyglycerin octanoate, polyglycerin decanoate, polyglycerin laurate, polyglycerin myristate , Polyglycerin esters such as polyglycerin palmitate, polyglycerin stearate, polyglycerin oleate, polyglycerin behenate; Sorbitan esters such as sorbitan acid ester, sorbitan octanoate, sorbitan decanoate, sorbitan laurate, sorbitan myristate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, and sorbitan behenate; (Poly) glycerin monooctyl ether, (poly) glycerin monodecyl ether, (poly)
(Poly) glycerin ethers such as glycerin monolauryl ether, (poly) glycerin monooleyl ether, (poly) glycerin monostearyl ether; ethylene oxide, propylene oxide,
Those to which an α-olefin oxide such as dodecane-1,2-oxide is added are exemplified. The preferred amount of the component (D8) is 0.05 to 10 with respect to the lubricating base material.
% By weight.

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 weight 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 / (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,
And a hydrogenated styrene / isoprene copolymer.
The average molecular weight is about 10,000 to 1,500,000. The preferred amount of the component (D10) is about 0.1 to 20% by weight 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 preferable blending amount of the component (D11) is about 0.01 to 5% by weight 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 weight 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 weight based on the lubricating base material.

The above component (D) can be used alone or in combination of two or more. When the lubricating composition of the present invention is used as a lubricating oil for an internal combustion engine, at least (D
It is preferable to mix 1) a metal detergent and (D6) an antioxidant.

The lubricating base material that can be used in the present invention includes a base oil composed of mineral oil, synthetic oil or a mixture thereof, a base grease containing a thickener mixed with such a base oil, and an aqueous lubricating oil. When used as a substrate, the substrate is water. 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 is preferably 1 to 5 at 100 ° C.
0mm ² / s, 40 ℃ in 10~1,000mm ² / s or so, viscosity index (VI) is preferably 100 or more, more preferably 120 or more, most preferably 135 or more.

The mineral oil used in the base oil of the present invention is separated from natural crude oil, and is produced by appropriately distilling, refining, and the like. Mineral oil is mainly composed of hydrocarbons (mostly paraffins), and also contains monocyclic naphthenes, bicyclic naphthenes, aromatics, and the like. These are hydrorefined, solvent removed, solvent extracted, solvent dewaxed,
Hydrodewaxing, catalytic dewaxing, hydrocracking, alkali distillation,
Base oils that have been subjected to purification such as sulfuric acid washing and clay treatment can also be preferably used. 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 in which a distillate is subjected to a solvent extraction treatment or a solvent extraction treatment followed by a hydrogenation treatment and then a sulfuric acid washing, (B) a method in which a distillate oil is subjected to a hydrogenation treatment and then a dewaxing treatment, (C) a method of subjecting a distillate to solvent extraction and then hydrotreating, (D) a method of subjecting a distillate to solvent extraction and a clay treatment, and (E) a distillate of two or more stages of hydrogen. (F) Hydrotreating distillate oil, or alkali distilling or sulfuric acid washing treatment after hydrogenation treatment, or these treatments A method of mixing oil 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 current 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 weight or less, and in some cases 0.005% by weight or less.
On the other hand, the aromatic component is 1% by weight or less, and in some cases, 0.1% by weight.
Some of them have a content of not more than 05% by weight and others have a content of about 3% by weight.

The synthetic oil used in the base oil of the present invention is
A chemically synthesized lubricating oil, such as poly-α-
Examples include olefin, polyisobutylene (polybutene), diester, polyol ester, aromatic polycarboxylic acid ester, phosphate ester, silicate ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, and alkylbenzene. Among them, poly-α-olefin, polyisobutylene (polybutene), diester, polyol ester, polyalkylene glycol and the like can be used for general purposes, and can be preferably used for internal combustion engine oil, processing oil and the like.

As 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 is therefore 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 mixture of the aforementioned base oil and a thickener is used as the 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. Although the amount of the thickener is not particularly limited, it is usually preferably 3 to the base grease comprising the base oil and the thickener.
-40% by weight, more preferably 5-20% by weight.
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 content of the alkali metal in the lubricating composition of the present invention is preferably not more than 0.02% by weight based on the total amount of the alkali metal contained in the lubricating composition.
It is more preferable that the content be 01% by weight 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.

Further, 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.
% By weight, more preferably 0.03% by weight or more, and most preferably 0.05% by weight or more. 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 for any purpose. 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.

[0097]

The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified.

Production of component (B): The phosphate and phosphite of component (B) used in the present invention were produced by the following method.

(Production of phosphoric acid ester) To 3 mol of 2-ethylhexanol, 1 mol of diphosphorus pentoxide was gradually added at 100 ° C. or lower. After aging at 60 to 100 ° C. for 2 hours, 3 mol of water was added. Hydrolysis was performed to obtain an acidic phosphate ester. 3 mol of ethylene oxide was added to the obtained acidic phosphate ester at 80 to 150 ° C. in an autoclave, and the mixture was aged for 2 hours at the same temperature to obtain a product 1 of the present invention. Less than,
Similarly, inventive products 2 to 5 and comparative products 1 and 2 were produced.

(Production of phosphite) 2 mol of phosphorous acid was dehydrated with 3 mol of lauryl alcohol at 140 ° C. for 5 hours under reduced pressure to obtain a phosphite. The obtained phosphite is autoclaved to 80 to 15
At 0 ° C., 3 mol of ethylene oxide was added, and
After aging for a time, a product 6 of the present invention was obtained. Similarly, a product 7 of the present invention and comparative products 3 to 4 were produced. Table 1 shows the obtained phosphate esters and phosphite esters.

[0101]

[Table 1]

[0102] Example: As the base oil, kinematic viscosity at 100 ° C. has a kinematic viscosity of ^{4.1mm 2 / s, 40 ℃ 18.3mm} 2 / s
Using a refined mineral oil, the following organic molybdenum compound of the following component (A) and the (phosphite) phosphate of the component (B) shown in Table 1 at the ratios shown in the following Tables 2-1 to 2-3 A lubricating composition was prepared by blending. These lubricating compositions were evaluated for lubricity and corrosivity by the following methods.

<Component (A)> Mo compound 1: In the general formula (1), R ^{1 to} R ⁴ = 2-
Ethylhexyl group, S / O of X ^{1 to} X ⁴ = 2.5 / 1.5
MoDTC. Mo compound 2: In the general formula (2), R ^{5 to} R ⁸ = 2-
Ethylhexyl group, S / O of X ^{1 to} X ⁴ = 2.5 / 1.5
MoDTP. Mo compound 3: In the general formula (1), R ^{1 to} R ⁴ = 2-
Ethylhexyl group and isotridecyl group = 1/1, X ¹
S / O = 2.5 / 1.5 in a MoDTC in to X ^4. Mo compound 4: In the general formula (1), R ^{1 to} R ⁴ = n-
Butyl group, X ^{1 to} X ⁴ S / O = 2.5 / 1.5 M
oDTC. Mo compound 5: a molybdenum amine reactant obtained by reacting a secondary amine in which R ⁹ and R ^{10 are} isotridecyl groups in the general formula (3) with 2 moles per 1 mole of molybdenum trioxide.

<Method of Measuring Friction Coefficient> With respect to the lubricating oil compositions shown in Table 2 below, the friction coefficient was measured using a SRV measuring tester under the line contact conditions of a cylinder-on-plate. Upper cylinder is φ15 × 22mm, plate is φ24 ×
6.85 mm, the cylinder was set on the plate perpendicular to the sliding direction, and the cylinder was reciprocated to measure the friction coefficient. Both cylinder and plate are made of SUJ
-2. Detailed measurement conditions are as follows. Conditions: Load: 200 N Temperature: 80 ° C. Measurement time: 7 minutes Amplitude: 1.0 mm Cycle: 50 Hz

<Corrosion Test> A test piece of cast iron was immersed in half in each of the lubricating oil compositions shown in Tables 2-1 to 2-3 and heated at 100 ° C. for 3 hours. Was observed, and the corrosion state was evaluated according to the following criteria. ：: No corrosion ×: Corrosion These evaluation results are shown in Tables 2-1 to 2-3.

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

The effect of the present invention is to provide a lubricating composition which hardly corrodes metals and has good extreme pressure properties.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10N 30:06 C10N 30:06 30:12 30:12 40:25 40:25 (72) Inventor Naoto Namiki Asahi Denka Kogyo Co., Ltd. F-term (reference) 4H104 BE02R BG10C BG12C BG15C BG19C BH02C BH03C BH04C BH05C BH07C BH11C CG09C DB04C EB03 EB11 EB07 EB09 FA03 EB09

Claims (4)

[Claims] 1. A lubricating base material comprising: an organic molybdenum compound as a component (A); and a general formula (B) represented by the following formula (B) as a component (B): (Wherein, R ^a , R ^b and R ^c represent a hydrocarbon group, m represents a number of 0 or 1 or more, k represents a number of 1 or more,
n represents a number of 1 to 2, and p represents 0 or 1. A) a lubricating composition comprising: 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 (D8) Oiliness improver not containing a metal atom, phosphorus atom and sulfur atom (D9) Rust inhibitor (D10) Viscosity index improver (D11) Metal deactivator (D12) Antifoaming agent (D13) Solid lubricant It contains one or more types of any one of Claims 1-3. Lubricating composition.