JPH11323368A - Turbine oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which maintains rust prevention and shows improved oxidative stability by making the composition contain a mineral oil-based lubricating base oil containing not less than a specific amount of a basic nitrogen, an aromatic amine-based anti-oxidant and a benzotriazole and/or a derivative thereof. SOLUTION: A turbine oil composition comprises not less than 90 mass % of a mineral oil-based lubricating base oil containing not less than 2 ppm of a basic nitrogen, 0.1-5.0 mass % of an aromatic amine-based antioxidant selected from a (N-p-alkyl)phenyl-α-naphtylamine represented by formula I or a p,p'-dialkyldiphenylamine represented by formula II and 0.001-1.0 mass % of a benzotriazole represented by formula III and/or a derivative thereof. The composition further contains 0.001-1.0 mass % of a rust preventive agent selected from a succinic acid having a 6-100C alkyl or alkenyl group or the like, a part ester from a polyvalent alcohol and a 10-22C fatty acid, an alkali metal sulfonate and the like (R' is H or an 1-16 C alkyl group; and R2 and R3 are 1-16C alkyl groups).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to turbine oil compositions and, more particularly, to turbine oil compositions having very good oxidation stability.

[0002]

2. Description of the Related Art Conventionally, an aromatic amine-based antioxidant such as phenyl-α-naphthylamine (PAN) is sometimes blended with turbine oil in order to improve its oxidation stability. In addition, in order to improve the rust prevention,
The use of a rust inhibitor typified by an alkenyl succinate or the like is also commonly used. However, when a mineral oil-based lubricating base oil containing a basic nitrogen content of 2 mass ppm or more and containing a basic nitrogen content to a certain degree or more is used as the base oil of the turbine oil, an aromatic amine antioxidant is used. The effect of the addition of iron is remarkably reduced, and no turbine oil having satisfactory oxidation stability has been produced. Even if the amount of the aromatic amine-based antioxidant added is increased to improve the oxidation stability, such a mineral oil-based lubricating base oil has a high oxidation stability when the turbine oil is used. However, there is a problem that the deterioration of the properties, that is, the shortening of the life of the aromatic amine antioxidant is fast. Further, when an aromatic amine-based antioxidant and a rust inhibitor are used in combination with a mineral oil-based lubricating base oil containing basic nitrogen to a certain extent, the rust inhibitor adversely affects the oxidation stability. ,
There is a major problem that the oxidation stability is deteriorated as compared with the system without the rust inhibitor.

[0003] Therefore, conventionally, in order to obtain a turbine oil having excellent oxidation stability, a high-level refining treatment such as hydrorefining, sulfuric acid washing, and clay treatment is performed to reduce the basic nitrogen content to 2%.
Means must be taken to use a mineral oil-based lubricating base oil reduced to less than ppm by mass.

[0004]

However, in order to perform such a high-level refining treatment on a lubricating base oil, large-scale equipment, use of a large amount of chemicals, and consumption of a large amount of energy are required. . In addition, even when a highly refined mineral oil-based lubricating base oil containing substantially zero basic nitrogen is used, a decrease in oxidation stability due to the combined use of an aromatic amine-based antioxidant and a rust inhibitor cannot be prevented. It is a fact.

Therefore, the basic nitrogen content is 2 mass ppm.
The development of a simpler method that can obtain a turbine oil having high oxidation stability even when a mineral oil-based lubricating base oil containing a certain amount or more of basic nitrogen is used is desired. Further, in turbine oil containing an aromatic amine-based antioxidant, development of means for preventing a decrease in oxidation stability when a rust inhibitor is used in combination is desired.

Accordingly, an object of the present invention is to use a mineral oil-based lubricating base oil containing 2 mass ppm or more of basic nitrogen, and to use a mineral oil-based lubricating base oil having substantially zero basic nitrogen content as an aromatic compound. An object of the present invention is to provide a turbine oil composition having oxidation stability that is equal to or higher than that of a turbine oil composition containing a group III amine-based antioxidant. Another object of the invention is
Using a mineral oil-based lubricating base oil containing 2 mass ppm or more of basic nitrogen, an aromatic amine-based antioxidant and a rust inhibitor are added to a mineral oil-based lubricating base oil having a basic nitrogen content of substantially zero. Another object of the present invention is to provide a turbine oil composition further improved in oxidation stability while maintaining the same rust-preventing performance as compared with a turbine oil composition containing the same.

[0007]

Means for Solving the Problems The present inventors have conducted research to solve the above problems, and as a result, the aromatic lubricating base oil containing 2 ppm by mass or more of basic nitrogen has been compared with the aromatic lubricating base oil. The present inventors have found that the above problems can be solved by combining and using an amine antioxidant and a specific nitrogen-containing compound, and have completed the present invention. Furthermore, 2 mass pp
When a mineral oil-based lubricating base oil containing basic nitrogen of at least m is used in combination with an aromatic amine-based antioxidant and a specific nitrogen-containing compound, even if a rust inhibitor is added, oxidation occurs. It has been found that the oxidation stability is improved without decreasing the stability, and the present invention has been completed. That is,
According to the present invention, (A) a mineral oil-based lubricating base oil having a basic nitrogen content of 2 mass ppm or more, (B) an aromatic amine-based antioxidant, (C) benzotriazole and / or a derivative thereof There is provided a turbine oil composition comprising: According to the present invention, (A) a mineral oil-based lubricating base oil having a basic nitrogen content of 2 mass ppm or more, (B) an aromatic amine-based antioxidant, and (C) benzotriazole and / or a derivative thereof And (D) a rust inhibitor.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in more detail. The mineral oil-based lubricating base oil used as the component (A) used in the present invention has a basic nitrogen content of 2 mass ppm or more, usually 5 mass ppm or more. Other properties of the mineral oil-based lubricating base oil are not particularly limited as long as the content of basic nitrogen is within the above range, and any mineral oil-based base oil that is usually used as a base oil for a lubricating oil can be used. Such 2
A major feature of the present invention is that a turbine oil composition having excellent oxidation stability can be easily obtained even when a mineral lubricating base oil containing basic nitrogen of mass ppm or more is used.

As the mineral oil-based lubricating base oil, for example,
The lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, dissolution dewaxing,
A paraffinic or naphthenic oil can be used which is purified by appropriately combining refining treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. These base oils may be used alone or in combination of two or more kinds at an arbitrary ratio. Wherein the viscosity of the mineral lubricating oil base oil is optional, usually, it is preferably from 1 to 1000 mm ² / s viscosity at 40 ℃, 5~800mm ² / s is more preferable. Also,
The viscosity index of the mineral oil-based lubricating base oil is also optional, but is usually preferably 85 or more, more preferably 100 or more.
In the present invention, the basic nitrogen content refers to UOP Method 2
“NITROGEN BASES IN HYDROCARBONS specified in 69-90
BY POTENTIOMETRIC TITRATION ”, basic organic nitrogen content in petroleum fractions
trogen), which usually includes heteroaromatic compounds such as pyridines and quinolines.

In the turbine oil composition of the present invention, the content of the component (A), which is a base oil, is arbitrary as long as it is an amount as a base oil.
% By mass, preferably 90 to 99.8% by mass.

The component (B) used in the present invention is an aromatic amine-based antioxidant. As the aromatic amine-based antioxidant, any aromatic amine-based compound used as an antioxidant for a lubricating oil can be used and is not particularly limited. For example, it is represented by the following formula (1) (N-p -Alkyl) phenyl-α-naphthylamine or one or more aromatic amine compounds selected from p, p'-dialkyldiphenylamine represented by the following formula (2).

[0012]

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(Wherein R ¹ is a hydrogen atom or a C ¹ -C 1)
6 represents a linear or branched alkyl group. R ² and R ³
Is the same or different and represents an alkyl group having 1 to 16 carbon atoms. ) (Np-alkyl) phenyl-α represented by the formula (1)
- In naphthylamine, the proportion of the functional group occupying in the molecule is small when the number of carbon atoms of R ¹ exceeds 16,
The antioxidant ability may be weakened. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a linear or branched pentyl group. A straight-chain or branched hexyl group, a straight-chain or branched heptyl group, a straight-chain or branched octyl group, a straight-chain or branched nonyl group, a straight-chain or branched A branched decyl group, a linear or branched undecyl group, a linear or branched dodecyl group, a linear or branched tridecyl group, a linear or branched tetradecyl group, Examples thereof include a linear or branched pentadecyl group and a linear or branched hexadecyl group. Among these alkyl groups, the (A)
A branched alkyl group having 8 to 16 carbon atoms is preferable in view of excellent solubility of the oxidation product itself to the component, and further, a branched alkyl group having 8 to 16 carbon atoms derived from an oligomer of an olefin having 3 or 4 carbon atoms is preferable. Branched alkyl groups are more preferred. Here, specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene and isobutylene, but the solubility of the oxidation product of itself with respect to the component (A) is limited. Propylene or isobutylene is preferred from the viewpoint of superiority. As the aromatic amine-based antioxidant (B) used in the present invention, (N-
When p-alkyl) phenyl-α-naphthylamine is used, R ¹ is a hydrogen atom or a branched octyl group derived from a dimer of isobutylene, and a branched nonyl derived from a trimer of propylene. Group, isobutylene 3
A branched dodecyl group derived from a dimer, a branched dodecyl group derived from a propylene tetramer or a branched pentadecyl group derived from a pentamer of propylene is particularly preferred, and a hydrogen atom or a dimer of isobutylene is particularly preferred. The most preferred is a branched octyl group derived from a trimer of isobutylene, a branched dodecyl group derived from a trimer of isobutylene, or a branched dodecyl group derived from a tetramer of propylene.

As the aromatic amine compound represented by the formula (1), R ¹ is an N-p-alkyl group having ¹ to 16 carbon atoms.
Alkylphenyl-α-naphthylamine is phenyl-
α-naphthylamine and an alkyl halide compound having 1 to 16 carbon atoms, an olefin having 2 to 16 carbon atoms or an olefin oligomer having 2 to 16 carbon atoms, and phenyl-α
-Can be easily synthesized by reacting with naphthylamine using a Friedel-Crafts catalyst.
As the Friedel-Crafts catalyst at this time, for example,
Metal halides such as aluminum chloride, zinc chloride and iron chloride; and acid catalysts such as sulfuric acid, phosphoric acid, phosphorus pentoxide, boron fluoride, acid clay, activated clay and the like can be used.
Moreover, a commercial item can also be used for Np-alkylphenyl-α-naphthylamine.

In the p, p'-dialkyldiphenylamine represented by the formula (2), when one or both of R ² and R ³ is a hydrogen atom, there is a possibility that the compound itself may precipitate as sludge by oxidation. When the number of carbon atoms exceeds 16, the proportion of the functional group in the molecule becomes small, and the antioxidant ability may be weakened. As R ² and R ^{3 in} the formula (2), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, linear Or a branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a linear or branched nonyl Group, straight-chain or branched decyl group, straight-chain or branched undecyl group, straight-chain or branched dodecyl group, straight-chain or branched tridecyl group, straight-chain or A branched tetradecyl group,
Examples thereof include a linear or branched pentadecyl group and a linear or branched hexadecyl group. Among these alkyl groups, a branched alkyl group having 3 to 16 carbon atoms is preferable from the viewpoint of excellent solubility of the oxidation product itself to the component (A), and further, an olefin having 3 or 4 carbon atoms or A branched alkyl group having 3 to 16 carbon atoms derived from the oligomer is more preferred. Here, specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene, and isobutylene, and are excellent in solubility of an oxidation product of itself in a lubricating base oil. From the viewpoint, propylene or isobutylene is preferred. When p, p'-dialkyldiphenylamine represented by the formula (2) is used as the aromatic amine antioxidant (B) used in the present invention, R ² and R ³ are derived from propylene. Tert-butyl groups derived from isobutylene, branched hexyl groups derived from propylene dimer, branched octyl groups derived from isobutylene dimer, and propylene trimers. A branched nonyl group, a branched dodecyl group derived from a trimer of isobutylene, a branched dodecyl group derived from a tetramer of propylene, or a branched pentadecyl group derived from a pentamer of propylene is particularly preferred. Tert-butyl group derived from isobutylene, branched hexyl group derived from propylene dimer, derived from isobutylene dimer Branched octyl, branched nonyl group derived from propylene trimer, a branched dodecyl group derived from isobutylene trimer, a branched dodecyl group derived from a tetramer of propylene are most preferred.

The p, p'-dialkyldiphenylamine represented by the formula (2) is obtained by combining diphenylamine with C1-C1.
And a halogenated alkyl compound having 6 to 2 carbon atoms.
6 or an olefin having 2 to 16 carbon atoms or an oligomer thereof and diphenylamine by Friedel
It can be easily synthesized by reacting with a crafts catalyst. As the Friedel-Crafts catalyst at this time, the above-mentioned metal halides, acidic catalysts and the like can be used. Moreover, a commercial item can also be used for p, p'-dialkyldiphenylamine.

In the present invention, the compound represented by the formula (1) or (2) may be used alone as the aromatic amine-based antioxidant (B), or the compound represented by the formula (1) A mixture in which two or more compounds represented by the formula (2) are mixed in an arbitrary ratio, a mixture in which two or more compounds represented by the formula (2) are mixed in an arbitrary ratio, one or more compounds represented by the formula (1) It can also be used as a mixture or the like in which one or more compounds represented by the formula (2) are mixed at an arbitrary ratio.

The content of the component (B) in the turbine oil composition of the present invention is arbitrary, but usually the lower limit of the content is preferably 0.1% by mass, based on the total amount of the turbine oil composition. Preferably it is 0.3% by mass. On the other hand, the upper limit of the content is preferably 5.0% by mass, more preferably 2.0% by mass. When the content of the component (B) is less than 0.1% by mass based on the total amount of the turbine oil composition, the effect of improving the oxidation stability due to the component (B) may not be sufficient. 5.0 based on the total amount of the oil composition
If the amount is more than% by mass, the effect of improving the oxidation stability corresponding to the content may not be obtained, which may be economically disadvantageous.

The component (C) used in the present invention is benzotriazole and / or a derivative thereof. Benzotriazole is a compound represented by the following formula (3).

[0020]

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Examples of the benzotriazole derivative include, for example, an alkylbenzotriazole represented by the following formula (4) and an (alkyl) aminoalkylbenzotriazole represented by the following formula (5).

[0022]

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In the above formula (4), R ⁴ represents a linear or branched alkyl group having 1 to ⁴ carbon atoms, preferably a methyl group or an ethyl group, and a represents 1 to 3, preferably 1 to 4. Or 2
Indicates the number of As R ⁴ , for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include an isobutyl group, a sec-butyl group, and a tert-butyl group. As the alkylbenzotriazole represented by the formula (4), R ⁴ is a methyl group or an ethyl group, and a is 1
Or 2 is preferable, and examples thereof include methylbenzotriazole (tolyltriazole), dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole, and a mixture thereof.

In the above formula (5), R ⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and R ⁶ represents a methylene group or an ethylene group. , R ⁷ and R ⁸ are the same or different groups, and are a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms,
It preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms, and b represents a number of 0 to 3, preferably 0 or 1. As R ⁵ , for example, a methyl group, an ethyl group,
Examples include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. As R ⁷ and R ⁸ , for example, separately, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a linear or Pentyl group on the branch,
Straight or branched hexyl group, straight or branched heptyl group, straight or branched octyl group, straight or branched nonyl group, straight or branched decyl group, straight or branched chain A undecyl group, a linear or branched dodecyl group, a linear or branched tridecyl group, a linear or branched tetradecyl group, a linear or branched pentadecyl group, a linear or branched hexadecyl group,
Examples of the alkyl group include a linear or branched heptadecyl group and a linear or branched octadecyl group.

As the (alkyl) aminobenzotriazole represented by the above formula (5), R ⁵ is a methyl group and b is 0 or 1 in view of particularly excellent antioxidant properties.
Wherein R ⁶ is a methylene group or an ethylene group, and R ⁷ and R ⁸ are linear or branched alkyl groups having 1 to 12 carbon atoms, such as dialkylaminoalkylbenzotriazole or dialkylaminoalkyltolyltriazole; These mixtures and the like are preferably used. Examples of these dialkylaminoalkylbenzotriazoles include dimethylaminomethylbenzotriazole, diethylaminomethylbenzotriazole, di (linear or branched) propylaminomethylbenzotriazole, and di (linear or branched) butylaminomethylbenzotriazole ,
Di (linear or branched) pentylaminomethylbenzotriazole, di (linear or branched) hexylaminomethylbenzotriazole, di (linear or branched) heptylaminomethylbenzotriazole, di (linear or branched) Octylaminomethylbenzotriazole, di (linear or branched)
Nonylaminomethylbenzotriazole, di (linear or branched) decylaminomethylbenzotriazole, di (linear or branched) undecylaminomethylbenzotriazole, di (linear or branched) dodecylaminomethylbenzotriazole; dimethyl Aminoethylbenzotriazole, diethylaminoethylbenzotriazole, di (linear or branched) propylaminoethylbenzotriazole, di (linear or branched) butylaminoethylbenzotriazole, di (linear or branched) pentylaminoethylbenzo Triazole, di (linear or branched) hexylaminoethylbenzotriazole, di (linear or branched) heptylaminoethylbenzotriazole, di (linear or branched) octylaminoethylbenzotriazole, di (linear or branched) Branch) Nonylami Ethyl benzotriazole,
Di (linear or branched) decylaminoethylbenzotriazole, di (linear or branched) undecylaminoethylbenzotriazole, di (linear or branched) dodecylaminoethylbenzotriazole; dimethylaminomethyltolyltriazole, diethylamino Methyltolyltriazole, di (linear or branched) propylaminomethyltolyltriazole, di (linear or branched) butylaminomethyltolyltriazole, di (linear or branched) pentylaminomethyltolyltriazole, di (linear) Or branched) hexylaminomethyltolyltriazole, di (linear or branched) heptylaminomethyltolyltriazole, di (linear or branched) octylaminomethyltolyltriazole, di (linear or branched) nonylaminomethyltolyl Triazole, di (linear or Branched) decylaminomethyltolyltriazole, di (linear or branched) undecylaminomethyltolyltriazole, di (linear or branched) dodecylaminomethyltolyltriazole; dimethylaminoethyltolyltriazole, diethylaminoethyltolyltriazole, di (Linear or branched) propylaminoethyltolyltriazole, di (linear or branched) butylaminoethyltolyltriazole, di (linear or branched) pentylaminoethyltolyltriazole, di (linear or branched) hexyl Aminoethyltolyltriazole, di (linear or branched) heptylaminoethyltolyltriazole, di (linear or branched) octylaminoethyltolyltriazole, di (linear or branched) nonylaminoethyltolyltriazole, di (direct Chain or branch) de Le aminoethyl tolyltriazole, di (straight or branched) undecyl aminoethyl tolyltriazole, di (straight or branched) dodecyl aminoethyl tolyltriazole; or mixtures thereof.

Although the content of the component (C) in the turbine oil composition of the present invention is arbitrary, the lower limit is usually preferably 0.001% by mass, based on the total amount of the turbine oil composition.
More preferably, it is 0.005% by mass. On the other hand, the upper limit is preferably 1.0% by mass, more preferably 0.5% by mass.
% By mass. When the content of the component (C) is less than 0.001% by mass based on the total amount of the turbine oil composition, the effect of improving the oxidation stability due to the component (C) may not be sufficient. 1.0% by mass based on the total amount of the composition
If it exceeds 3, the effect of improving the oxidation stability corresponding to the content may not be obtained, which may be economically disadvantageous.

Although the turbine oil composition of the present invention has excellent antioxidant properties and a long-lasting effect even when it is used as it is, it may further contain a rust inhibitor as a component (D) for the purpose of improving its rust inhibiting performance. Can be.

In the present invention, when the component (C) benzotriazole and / or a derivative thereof is not used, not only the case where the component (A) of the present invention is used as a base oil, but also the case where the basic nitrogen content is lower. Even when a mineral oil-based lubricating base oil having a high purity of substantially zero is used and a rust inhibitor is added, the rust inhibitor adversely affects oxidation stability. However, according to the invention, the basic nitrogen content is 2 mass pp
m or more, even when a low-purity mineral oil-based lubricating base oil is used, the combination of component (C) and component (D) results in a turbine oil composition that has both excellent oxidation stability and rust resistance. It is possible to get things.

As the component (D) of the present invention, any additive usually used as a rust preventive for lubricating oil can be used, but it has little adverse effect on the demulsifying performance and is excellent in rust preventive performance. From the viewpoint, one or more compounds selected from the following are preferably used. Succinic acid and / or ester thereof having an alkyl or alkenyl group having 6 to 100 carbon atoms Partial ester of polyhydric alcohol and fatty acid having 10 to 22 carbon atoms Alkali metal salt and / or alkaline earth metal salt of sulfonic acid.

Examples of the succinic acid having an alkyl group or an alkenyl group having 6 to 100 carbon atoms include a compound represented by the following formula (6) or an anhydride thereof.

[0031]

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In the above formula (6), R ⁹ is a group having 6 to 10 carbon atoms.
0, preferably an alkyl group or alkenyl group having 8 to 80 carbon atoms. The method for producing the succinic acid having an alkyl group or an alkenyl group is not limited at all, and for example, a polyolefin such as a propylene oligomer having 6 to 100 carbon atoms, preferably 8 to 80 carbon atoms, polybutene, ethylene-propylene copolymer, or the like, may be anhydro- It can be easily obtained by a method of reacting with maleic acid.

Examples of the ester of succinic acid having an alkyl group or an alkenyl group having 6 to 100 carbon atoms include succinic acid or an anhydride thereof represented by the above formula (6), , Preferably having 1 carbon atom
To 22 monovalent aliphatic monoalcohols or esterified products with 2 to 50 carbon atoms of a polyhydric alcohol. The aliphatic monoalcohol having 1 to 30 carbon atoms may be a linear aliphatic monohydric alcohol or a branched aliphatic monohydric alcohol. Further, it may be a saturated aliphatic monohydric alcohol or an unsaturated aliphatic monohydric alcohol. Specifically, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol , Hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, icosyl alcohol, henicosyl alcohol, docosyl alcohol, pentenyl alcohol, hexenyl alcohol, heptenyl alcohol, octenyl alcohol, nonenyl alcohol, decenyl Alcohol, undecenyl alcohol, dodecenyl alcohol, tridecenyl alcohol, tetradecenyl alcohol Kohl, pentadecenyl alcohol, hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, icosenyl alcohol, henicocenyl alcohol, docosenyl alcohol, octadeca And dienyl alcohol (however, those compounds having isomers include all isomers).

Examples of the polyhydric alcohol having 2 to 50 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, glycerin, trimethylolethane, Trimethylolpropane, pentaerythritol, sorbitan (however, those compounds having isomers include all isomers) and the like can be exemplified, as long as the number of carbon atoms is in the range of 2 to 50. Polyhydric alcohol dimer, trimer, tetramer or higher multimer, specifically, diethylene glycol, triethylene glycol, tetraethylene glycol or higher polyethylene glycol; dipropylene glycol, tripropylene glycol, tetrapropylene glycol Polypropylene glycol or higher; dibutylene glycol, tributylene glycol, tetramer or higher polybutylene glycol; diglycerin, triglycerin, tetramer or higher polyglycerin, di (trimethylolethane), tri (trimethylolethane) Poly (trimethylolethane), tetramer or higher; di (trimethylolpropane), tri (trimethylolpropane); tetra (or higher) poly (trimethylolpropane); di (pentaerythritol), tri (pentaerythritol) , Tetra (pentaerythritol); di (sorbitan), tri (sorbitan), and tetra (or more) poly (sorbitan).

Examples of the succinic acid ester having an alkyl group or an alkenyl group include a full ester in which two carboxyl groups in the succinic acid having an alkyl group or an alkenyl group are all esterified with a monoalcohol or a polyhydric alcohol. There is a half ester in which one carboxyl group is esterified with a monoalcohol or a polyhydric alcohol and the other remains in the form of a free acid. In the present invention, any of these half esters or a mixture thereof is used. Can be used. When a polyhydric alcohol, for example, a dihydric alcohol is used for the esterification, a so-called monotype succinic ester in which only one end of the dihydric alcohol is esterified with a succinic acid having an alkyl group or an alkenyl group is used. There are so-called bis-type succinic esters in which both ends of a hydric alcohol are esterified with a succinic acid having an alkyl group or an alkenyl group. In the present invention, any of these and a mixture thereof can be used.

As the compound, succinic acid having an alkyl or alkenyl group having 8 to 80 carbon atoms and an aliphatic monoalcohol having 1 to 22 carbon atoms or 2 to 50 carbon atoms are preferable in terms of excellent rust prevention performance. Polyhydric alcohol (2
Half-esters of succinic acid having an alkyl or alkenyl group having 8 to 80 carbon atoms and 2 to 5 carbon atoms.
A half ester with a polyhydric alcohol of 0 (including a polymer of a dihydric or higher polyhydric alcohol) is more preferable.

On the other hand, the above-mentioned polyhydric alcohol and C 1
As partial esters with fatty acids of 0 to 22, glycerin, trimethylolethane, trimethylolpropane,
Examples thereof include partial esters of one or more polyhydric alcohols selected from pentaerythritol and sorbitan with fatty acids having 10 to 22 carbon atoms. Here, the partial ester means an ester in which at least one or more of the hydroxyl groups in the polyhydric alcohol is not esterified and remains in the form of a hydroxyl group.

The fatty acid in the above may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. For example, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid,
Saturated fatty acids such as hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, etc .; Acid, nonadecenoic acid, eicosenoic acid, heneicosenoic acid,
Unsaturated fatty acids such as docosenoic acid (including all isomers of the above compounds), or a mixture thereof;
Octadecenoic acid is preferred from the viewpoint of excellent antirust performance, and oleic acid is particularly preferred.

Examples of the compound include glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, glycerin didodecanoate (glycerin dilaurate), glycerin diisolaurate, and glycerin monotetradecanoate ( Glycerin monomyristate), glycerin monoisomyristate, glycerin ditetradecanoate (glycerin dimyristate), glycerin diisomyristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, Glycerin dihexadecanoate (glycerin dipalmitate), glycerin diisopalmitate, glycerin monooctadecanoate (glycerin monostearate),
Glycerin monoisostearate, glycerin dioctadecanoate (glycerin distearate), glycerin diisostearate, glycerin monooctadesenoate (glycerin monooleate), glycerin monoisooleate, glycerin dioctadecenoate (Glycerin dioleate), glycerin partial ester such as glycerin diisooleate; trimethylolethane monododecanoate (trimethylolethane monolaurate), trimethylolethane monoisolaurate, trimethylolethanedidodecanoate ( Trimethylolethanedilaurate), trimethylolethanediisolaurate, trimethylolethane monotetradecanoate (trimethylolethane monomyristate), trimethylolethane ethane monoi Myristate, trimethylolethaneditetradecanoate (trimethylolethanedimyristate), trimethylolethanediisomyristate, trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisomate Palmitate, trimethylolethanedihexadecanoate (trimethylolethanedipalmitate), trimethylolethanediisopalmitate,
Trimethylolethane monooctadecanoate (trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylolethane dioctadecanoate (trimethylolethanedistearate), trimethylolethanediisostearate, Trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate, trimethylolethanedioctadecenoate (trimethylolethanedioleate), trimethylolethanediisooleate, etc. Trimethylolethane partial ester of trimethylolpropane monododecanoate (trimethylolpropane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropane Dodecanoate (trimethylolpropane dilaurate), trimethylolpropane di iso dilaurate, trimethylolpropane mono- tetradecanoate (trimethylolpropane monomyristate), trimethylolpropane monoisostearate myristate,
Trimethylolpropane ditetradecanoate (trimethylolpropane dimyristate), trimethylolpropane diisomyristate, trimethylolpropane monohexadecanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisopalmitate, Trimethylolpropane dihexadecanoate (trimethylolpropane dipalmitate), trimethylolpropane diisopalmitate, trimethylolpropane monooctadecanoate (trimethylolpropane monostearate), trimethylolpropane monoisostearate, Trimethylolpropane dioctadecanoate (trimethylolpropane distearate),
Trimethylolpropane diisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate, trimethylolpropane dioctadecenoate (trimethylolpropanedioleate), Trimethylolpropane partial esters such as trimethylolpropane diisooleate; pentaerythritol monododecanoate (pentaerythritol monolaurate), pentaerythritol monoisolaurate, pentaerythritol didodecanoate (pentaerythritol dilaurate), pentaerythritol Diisolaurate, pentaerythritol tridodecanoate (pentaerythritol trilaurate), pentaerythritol triiso Urate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomyristate, pentaerythritol ditetradecanoate (pentaerythritol dimyristate), pentaerythritol diisomyristate, pentaerythritol tritetralate Decanoate (pentaerythritol trimyristate), pentaerythritol triisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol dihexadecanoate (pentaerythritol) Dipalmitate), pentaerythritol diisopalmitate, pentaerythritol trihexadecano (Pentaerythritol tripalmitate), pentaerythritol triisopalmitate, pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol dioctadecanoate (pentaerythritol di Pentaerythritol diisostearate, pentaerythritol trioctadecanoate (pentaerythritol tristearate), pentaerythritol triisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate), pentaerythritol Monoisooleate, pentaerythritol dioctadecenoate (pentaerythritol dioleate), penta Pentaerythritol partial esters such as erythritol diisooleate, pentaerythritol trioctadecenoate (pentaerythritol trioleate), and pentaerythritol triisooleate;
Sorbitan monododecanoate (sorbitan monolaurate), sorbitan monoisolaurate, sorbitan didodecanoate (sorbitan dilaurate), sorbitan diisolaurate, sorbitan tridodecanoate (sorbitan trilaurate), sorbitan triisolaurate, Sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan monoisomyristate, sorbitan ditetradecanoate (sorbitan dimyristate), sorbitan diisomyristate, sorbitan tritetradecanoate (sorbitan trimyristate) , Sorbitan triisomyristate, sorbitan monohexadecanoate (sorbitan monopalmitate), sorbitan monoisopalmitate, sorbitan dihexadecanoate Sorbitan dipalmitate), sorbitan diisopalmitate, sorbitan trihexadecanoate (sorbitan tripalmitate), sorbitan triisopalmitate, sorbitan monooctadecanoate (sorbitan monostearate), sorbitan monoisostearate, Sorbitan dioctadecanoate (sorbitan distearate), sorbitan diisostearate, sorbitan trioctadecanoate (sorbitan tristearate), sorbitan triisostearate, sorbitan monooctadecenoate (sorbitan monooleate) Sorbitan monoisooleate, sorbitan dioctadecenoate (sorbitan dioleate), sorbitan diisooleate, sorbitan trioctadecenoate (sorbitan trio) Benzoate), sorbitan partial esters, such as sorbitan triisostearate oleate; or a mixture thereof are preferably used.

Further, glycerin monooleate, glycerin dioleate, trimethylolethane monooleate, trimethylolethanedioleate, trimethylolpropane monooleate, and trimethylolpropanediolate are excellent in anticorrosive performance. Pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate or a mixture thereof is more preferable, particularly glycerin monooleate, trimethylol, which is monooleate Preference is given to ethane monooleate, trimethylolpropane monooleate, pentaerythritol monooleate, sorbitan monooleate or mixtures thereof. Ku used.

Examples of the above-mentioned alkali metal salt and / or alkaline earth metal salt of sulfonic acid include alkali metal salts such as sodium salt and potassium salt of sulfonic acid, and alkaline earth salts such as magnesium salt, calcium salt and barium salt. Metal salts can be exemplified. The process for producing this compound is
There is no particular limitation, and those produced by any method can be used. For example, alkali metals of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, particularly 200 to 700 Salts, alkaline earth metal salts or mixtures thereof can be used.

The alkyl aromatic sulfonic acid is generally a sulfonated alkyl aromatic compound of a lubricating oil fraction of a mineral oil, a petroleum sulfonic acid such as so-called mahoganic acid, which is a by-product of white oil production, and a detergent, for example. Sulfonated alkylbenzene having a linear or branched alkyl group, obtained by alkylating polyolefin to benzene, or dinonylnaphthalene, etc. And synthetic sulfonic acids such as those obtained by sulfonating alkylnaphthalenes.

As the compound of the above, the alkyl aromatic sulfonic acid can be directly converted to an alkali metal base (eg, an oxide or hydroxide of an alkali metal) and / or an alkaline earth base (eg, an oxide or hydroxide of an alkaline earth metal). Product)), the neutral (normal salt) sulfonate and the basic sulfonate obtained by reacting the neutral (normal salt) sulfonate with an excess amount of an alkali metal base or alkaline earth metal in the presence of carbon dioxide gas. A carbonate overbased sulfonate or a neutral (normal salt) sulfonate produced by reacting with a base is reacted with an alkali metal base or an alkaline earth metal base, and a boric acid compound such as boric acid or boric anhydride. Borate overbased sulfonate and the like can be used.

In the compound of formula (I), the total base number determined by the perchloric acid method specified in JIS K 2501 is arbitrary, but is usually 0.
~ 500mgKOH / g, preferably 0 ~ 300mgK
Sulfonates having a base number of OH / g, more preferably 0-100 mg KOH / g, can be used.
In particular, from the point of excellent rust prevention performance, the total base number by the perchloric acid method specified in JIS K 2501 is 0 to 50 mg KOH.
/ G of a neutral (normal salt) sulfonate, more preferably a neutral (normal salt) barium sulfonate having a total base number of 0 to 50 mgKOH / g.

The component (D) used in the present invention is as described above.
A mixture obtained by mixing two or more compounds selected from the compounds in an arbitrary ratio can also be preferably used, but it is particularly preferable to use the compound in that the adverse effect on the demulsifying performance is less and the rust inhibiting performance is more excellent. preferable.

In the turbine oil composition of the present invention, (D)
When the components are used in combination, the content of the component (D) is arbitrary, but usually, the lower limit is preferably 0.001% by mass, more preferably 0.001% by mass, based on the total amount of the turbine oil composition.
5% by mass. On the other hand, the upper limit is preferably 1.0
%, More preferably 0.5% by mass. When the content of the component (D) is less than 0.001% by mass based on the total amount of the turbine oil composition, the effect of improving the rust-preventing property due to the component (D) may not be sufficient. If the amount exceeds 1.0% by mass based on the total amount of the oil composition, there is a possibility that the effect of improving the rust-preventing property corresponding to the content is not obtained, and it is economically disadvantageous.

In the turbine oil composition of the present invention, known lubricating oil additives may be used alone or in a combination of several types in order to further enhance various performances thereof. Known lubricating oil additives include, for example, phenol-based, sulfur-based, zinc dithiophosphate-based, phenothiazine-based antioxidants; phosphate esters, sulfurized fats, anti-wear agents such as zinc dithiophosphate; thiadiazole, benzothiazole Metal deactivators such as derivatives thereof; antifoaming agents such as methyl silicone and fluorosilicone; and pour point depressants such as polymethacrylate, polyisobutylene, olefin copolymer and polystyrene. The addition amount of these lubricating oil additives is arbitrary, but usually, based on the total amount of the turbine oil composition, the content of the defoamer is 0.0005 to 1% by mass, and the content of the metal deactivator is 0.005 to 1% by mass, and the content of other additives is 0.1 to 15% by mass, respectively.

[0048]

The turbine oil composition of the present invention has a mass of 2 mass p
Since a mineral oil-based lubricating base oil containing basic nitrogen of pm or more is used and an aromatic amine-based antioxidant and benzotriazole and / or a derivative thereof are blended, the basic nitrogen content is substantially zero. Higher oxidation stability equivalent to or higher than that of a turbine oil composition obtained by blending an aromatic amine antioxidant with a mineral oil-based lubricating base oil is obtained. Oxidation stability while maintaining equivalent rust prevention performance compared to a turbine oil composition containing an aromatic amine-based antioxidant and rust inhibitor in a mineral oil-based lubricating base oil with substantially zero amount Can be further improved.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Examples 1 to 7 Turbine oil compositions according to the present invention were prepared according to the compositions shown in Table 1 (Examples 1 to 5). For comparison, when the base oil was used alone (Comparative Example 1), when the component (C) was not used together (Comparative Example 2), when the component (D) was used together with Comparative Example 2 (Comparative Example 3), the base oil was used. When only a mineral oil-based lubricating base oil having a basic nitrogen content of 0 ppm was used as the base oil (Comparative Example 4),
When the component (B) was blended (Comparative Example 5, Comparative Example 6), and when the component (D) was used together with Comparative Example 5 (Comparative Example 7), a turbine oil composition was prepared according to the composition shown in Table 1. .

The components used in Table 1 are as follows. (A) Component A-1: Hydrocracked refined paraffinic mineral oil having a kinematic viscosity at 40 ° C. of 32 mm ² / s, a viscosity index of 130, and a basic nitrogen content of 32 mass ppm (B) Component B-1: Np -Branched dodecylphenyl-α-naphthylamine (the branched dodecyl group is derived from a propylene tetramer) B-2: p, p'-di-branched octidiphenylamine (the branched octyl group is derived from a dimer of isobutylene) (C) Component C-1:

[0051]

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C-2: Benzotriazole (D) Component D-1: C 9 derived from propylene oligomer
Half ester of alkenyl succinic acid having alkenyl group of -15 and dimer of propylene glycol D-2: sorbitan oleate (sorbitan mono, di,
Mixture of trioleate) Other base oil A-2: Hydrocracked refined paraffinic mineral oil having a kinematic viscosity at 40 ° C. of 32 mm ² / s, a viscosity index of 134, and a basic nitrogen content of 0 mass ppm. These Examples and Comparative Examples The turbine oil composition was subjected to the following oxidation stability test and rust prevention test. Table 1 shows the results. 5. Oxidation stability test JIS K 2514-1993 "Lubricating oil-Oxidation stability test method" 6. The "rotating cylinder-type oxidation stability test method" specified in, was performed, and the time required to reach the end point was measured. Rust prevention performance The rust prevention performance was evaluated in accordance with 7.2 "Rust prevention test method using artificial seawater" specified in JIS K 2510-1987 "Lubricant rust prevention performance test method".

[0053]

[Table 1]

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 129: 76 129: 74) C10N 30:00 30:10 30:12 40:25

Claims (2)

[Claims] (1) A mineral oil-based lubricating base oil having a basic nitrogen content of 2 mass ppm or more, (B) an aromatic amine-based antioxidant, and (C) benzotriazole and / or a derivative thereof. A turbine oil composition comprising: 2. A mineral oil base oil having a basic nitrogen content of 2 mass ppm or more, (B) an aromatic amine antioxidant, (C) benzotriazole and / or a derivative thereof,
(D) A turbine oil composition comprising a rust inhibitor.