JP5237562B2 - Lubricating oil composition for ceramic ball rolling bearing - Google Patents

Description

  The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition for lubricating ceramics.

In recent years, Japanese machine tool manufacturers have been trying to improve the performance and functionality of machine tools in order to meet the demands of customers and to differentiate them. In particular, in the machining center (MC), development of a machine tool that enables high-speed and high-precision machining is in progress. Since the main axis of 10,000 m ⁻¹ appeared for the first time in 1982, the speeding up of MC has been evolving every year. Recently, medium and large size MC exceeding 30,000 m ⁻¹ have been put into practical use. Technologies that have contributed to such high speeds include oil-air lubrication, ceramic balls, and low heat generation robust bearings.

  High-speed cutting significantly increases the thermal load on the rolling bearing and causes scoring and scuffing of the rolling bearing, which causes problems with oil-air lubricants used in these applications. There is a strong demand for wear and extreme pressure.

For these reasons, conventionally, as such lubricating oils, those having a predetermined base oil blended with an antioxidant, a rust inhibitor and a mild antiwear agent are known, but such lubricants are still insufficient. The effect was not obtained. (Patent Document 1)
Japanese Patent Application Laid-Open No. 5-320679

  As described above, when used in high-speed main shaft lubrication having a ceramic ball rolling bearing, the conventional lubricating oil cannot always be said to have sufficient cooling performance, wear resistance and extreme pressure. That is, for applications that require high cooling, high extreme pressure, wear resistance, and rust prevention, phosphorus-based extreme pressure agents such as trialkyl phosphates or sulfur-phosphorus-based electrodes such as alkylated thiophosphates. Lubricating oil to which Ca sulfonate, Ba sulfonate, etc. are added as a rust preventive agent is widely used. However, since the rust preventive agent has high adsorptivity to the metal surface, various extreme pressure agents are used. There is a high possibility of hindering the effect of improving the lubricating performance, and it is very difficult to achieve both rust prevention and extreme pressure properties.

  In particular, in applications where the lubricant is used at high temperatures, the sulfur-phosphorus extreme pressure agent generates a large amount of sludge when a thermal load is applied even if the amount of addition is small, reducing the cooling performance of the bearing. Tend. Therefore, it is difficult for the lubricating oil to which the sulfur-based extreme pressure agent is added to obtain sufficient cooling performance and sludge resistance performance in the high-speed main shaft bearing having the ceramic ball rolling bearing described above.

  On the other hand, phosphorus-based extreme pressure agents tend to generate less sludge than sulfur-based extreme pressure agents. However, when a phosphorus-based extreme pressure agent is used alone, the high-speed main spindle lubricant for the ceramic ball rolling bearing is used. It is difficult to obtain a high level of cooling and extreme pressure required for the above.

  The present invention has been made in view of such a situation, and even when used for a high-speed spindle of a machine tool having a ceramic ball rolling bearing that is operated in a high-speed and high-load severe environment. It is an object of the present invention to provide an excellent lubricating oil composition that exhibits sufficient cooling properties, has high rust prevention properties, a high level of thermal oxidation stability, and high extreme pressure properties.

The present inventors have made intensive studies to achieve the above object, the at least one base oil selected from mineral oil and / or synthetic oil, an amine and a saturated monocarboxylic acid having a carbon number of 12 to 30 By containing at least one additive selected from the group of acid amide, sarcosine acid or aspartic acid derivative obtained by reaction, a lubricating oil composition for ceramic lubrication is obtained.
Further, phosphorus-containing carboxylic acid, phosphorus-containing carboxylic acid ester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, phosphorous acid ester, phosphorothionate, thiophosphoric acid ester, thiophosphoric acid metal salt, thiocarbamic acid ester, Alternatively, by using a combination of at least one of the metal salts of thiocarbamic acid, a lubricating oil composition having excellent lubricity between ceramics and steel and excellent rust prevention can be obtained.
Moreover, it can be set as the lubricating oil composition which has a sufficiently long oxidation lifetime by containing an aromatic amine compound and a phenol type compound further.

  According to the lubricating oil composition of the present invention, even when used for a high-speed main shaft of a machine tool having a ceramic ball rolling bearing machined in a severe environment of high temperature and high load, excellent low Friction characteristics and cooling properties (suppressing oil temperature rise) can be obtained. In addition, it is possible to exhibit a sufficiently long oxidation life as a lubricating oil and to maintain a high level of wear resistance and extreme pressure. Therefore, the lubricating oil composition of the present invention is very useful in that it can achieve high machining accuracy by suppressing the heat generation of the high-speed main spindle having the ceramic ball rolling bearing of the machine tool, and by stabilizing the thermal displacement of the machine tool. It is.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description, when a compound or a functional group can take both a linear structure and a branched structure, the compound includes both a linear structure and a branched structure unless otherwise specified. It is.

The lubricating oil composition of the present invention contains at least one base oil selected from mineral oil and synthetic oil.
As mineral oil, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing And oils such as paraffinic oils purified by appropriately combining purification treatments such as clay treatment.

As the base oil of these lubricating oil compositions, mineral oils and synthetic oils called highly refined base oils can be used. In particular, group 1 and group 2 in the API (American Petroleum Institute, American Petroleum Institute) base oil category. Base oils belonging to Group 3, Group 4, Group 5, etc. can be used alone or as a mixture.
The base oil used here has a total sulfur content of 1 mass% or less, preferably 500 mass ppm or less, more preferably 300 mass ppm or less, and even more preferably 50 mass ppm or less. The density at 15 ° C. is 0.8 to 0.9 g / cm ³ , preferably 0.8 to 0.865 g / cm ³ , more preferably 0.81 to 0.84 g / cm ³ . The aromatic content should be less than 3%, preferably less than 2%, more preferably less than 0.1%.

  Group 1 base oils include, for example, paraffinic mineral oil obtained by applying a suitable combination of refining means such as solvent dewaxing to a lubricating oil fraction obtained by distilling crude oil under reduced pressure. Can be mentioned.

For Group 2 base oils, for example, paraffinic mineral oil obtained by appropriately combining refining means such as hydrocracking and dewaxing for lubricating oil fractions obtained by atmospheric distillation of crude oil There is. Group 2 base oils refined by hydrorefining methods such as the Gulf Company method have a total sulfur content of less than 10 ppm by mass and an aromatic content of 5% or less, which is suitable for the present invention. The viscosity of these base oils is not particularly limited, but the viscosity index is 80 to 120, preferably 100 to 120. The kinematic viscosity at 40 ° C. is preferably ² to 680 mm ² / s, more preferably 8 to 220 mm ² / s. The total sulfur content is less than 300 ppm by mass, preferably less than 200 ppm by mass, more preferably less than 10 ppm by mass. The total nitrogen content is also less than 10 ppm by mass, preferably less than 1 ppm by mass. Furthermore, the aniline point should be 80 to 150 ° C, preferably 100 to 135 ° C.

Group 3 base oils and Group 2 plus base oils are produced, for example, by paraffinic mineral oils produced by advanced hydrorefining of lubricating oil fractions obtained by atmospheric distillation of crude oil or by dewaxing processes. Also suitable are base oils refined by the ISODEWAX process for converting and dewaxing the wax to be converted to isoparaffin, and base oils refined by the mobile WAX isomerization process. The viscosity of these base oils is not particularly limited, but the viscosity index is 95 to 145, preferably 100 to 140. The kinematic viscosity at 40 ° C. is preferably ² to 680 mm ² / s, more preferably 8 to 220 mm ² / s. The total sulfur content is 0 to 100 ppm by mass, preferably less than 10 ppm by mass. The total nitrogen content is also less than 10 ppm by mass, preferably less than 1 ppm by mass. Furthermore, it is good to use an aniline point of 80-150 degreeC, Preferably it is 110-135 degreeC.

GTL (Gas Liquid) synthesized by the Fischer-Tropsch method, which is a natural gas liquid fuel technology, has a very low total sulfur content and aromatic content compared to mineral oil base oil refined from crude oil. Since the ratio is extremely high, the oxidation stability is excellent and the evaporation loss is very small. Therefore, it is suitable as the base oil of the present invention. The viscosity property of the GTL base oil is not particularly limited, but usually the viscosity index is 130 to 180, more preferably 140 to 175. Moreover, kinematic viscosity in 40 degreeC is 2-680 mm < ² > / s, More preferably, it is 5-120 mm < ² > / s. In general, the total sulfur content is less than 10 mass ppm and the total nitrogen content is less than 1 mass ppm. An example of such a GTL base oil product is SHELL XHVI®.

  Group 4 base oils include, for example, polyolefins, and group 5 base oils include, for example, alkylbenzene, alkylnaphthalene, ester, polyoxyalkylene glycol, polyphenyl ether, dialkyl diphenyl ether, fluorine-containing compounds (perfluoropolyether, fluorinated). Polyolefin) and synthetic oils such as silicone oil.

The polyolefin includes polymers of various olefins or hydrides thereof. Any olefin may be used, and examples thereof include ethylene, propylene, butene, and α-olefins having 5 or more carbon atoms. In the production of polyolefin, one of the above olefins may be used alone, or two or more may be used in combination. Particularly preferred are polyolefins called polyalphaolefins (PAO).
The viscosity of these synthetic base oils is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably ² to 680 mm ² / s, more preferably 8 to 220 mm ² / s.

  The content of the base oil in the lubricating oil composition of the present invention is not particularly limited, but is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably based on the total amount of the lubricating oil composition. Is 95% by mass or more.

  The base oil contains at least one additive selected from acid amides, sarcosine acid, and aspartic acid derivatives to form a lubricating oil composition. This additive mainly has a rust prevention effect.

The acid amide is preferably an acid amide compound obtained by reacting a saturated monocarboxylic acid having 12 to 30 carbon atoms with an amine, such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, isostearic acid amide, etc. Is mentioned. In addition, polyalkylene polyamides obtained by reacting with polyalkylamines, for example, carboxylic acid amides such as isostearic acid triethylenetetramide, isostearic acid tetraethylenepentamide, and isostearic acid pentaethylenehexamide can also be suitably used.

（上記式１中、Ｒは炭素数１〜３０の直鎖状若しくは分枝状のアルキル基、アルケニル基を示す。） The sarcosine acid is a derivative of glycine represented by the following general formula 1.

(In the above formula 1, R represents a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms.)

Specific examples of the sarcosine acid include (Z) -N-methyl-N- (1-oxo-9-octadecenyl) glycine represented by the following formula 2.

The above aspartic acid derivative is represented by the following general formula 3.

In the general formula 3, X ₁ and X ₂ are each hydrogen, the same or different alkyl group having 3 to 6 carbon atoms, or a hydroxyalkyl group, more preferably a 2-methylpropyl group or a tertiary butyl group. Is good.
X ₃ is an alkyl group consisting of 1 to 30 carbon atoms, an alkyl group having an ether bond, or a hydroxyalkyl group. For example, an octadecyl group, an alkoxypropyl group, a 3-hydrocarbonoxyalkyl group having 6 to 18 carbon atoms and an alkyl group having 3 to 6 carbon atoms, more preferably a cyclohexyloxypropyl group, 3- Octyloxypropyl group, 3-isooctyloxypropyl group, 3-decyloxypropyl group, 3-isodecyloxypropyl group, 3-dodecyloxypropyl group, 3-tetradecyloxycypropyl group, 3-hexadecyloxysilane A propyl group is preferred.
X ₄ is a saturated or unsaturated carboxylic acid group consisting of 1 to 30 carbon atoms, an alkyl group consisting of 1 to 30 carbon atoms, an alkenyl group, or a hydroxyalkyl group. For example, a propionic acid group or a propionyl acid group is preferable.

  The aspartic acid derivative has an acid value defined by JIS K2501 of 10 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g. The aspartic acid derivative is used in the lubricating oil composition at about 0.01 to 5% by mass, preferably about 0.05 to 2% by mass.

  The content of the acid amide, sarcosine acid, aspartic acid derivative and the like is not particularly limited, but is 0.01 to 5% by mass, preferably 0.05 to 4.5% by mass, based on the total amount of the lubricating oil composition. More preferably, it is 0.05-4 mass%, More preferably, it is 0.05-3.5 mass%, More preferably, it is 0.05-3 mass%. When these contents are less than 0.01% by mass, the rust prevention property may be insufficient. On the other hand, when the content exceeds 5% by mass, the demulsibility and foaming property may be deteriorated.

  A phosphorus compound can be added to the lubricating oil composition of the present invention, thereby further imparting wear resistance and extreme pressure. Examples of the phosphorus compound suitable for the present invention include phosphorus-containing carboxylic acid, phosphorus-containing carboxylic acid ester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, phosphite ester, phosphorothionate, and metal thiophosphate. , Thiocarbamic acid metal salts, thiocarbamic acid esters, and the like. These phosphorus compounds can be used alone or in combination within a range of 0.01 to 2% by mass with respect to 100% by mass of the base oil.

  The phosphorus-containing carboxylic acid compound such as a phosphorus-containing carboxylic acid and the same ester may contain both a carboxyl group and a phosphorus atom in the same molecule, and the structure is not particularly limited. However, phosphorylated carboxylic acid or phosphorylated carboxylic acid ester is preferable from the viewpoint of extreme pressure and heat / oxidation stability.

  Examples of the phosphorylated carboxylic acid and phosphorylated carboxylic acid ester include compounds represented by the following formula (4).

（式（４）中、Ｒ4及びＲ5は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３０の炭化水素基を示し、Ｒ6は炭素数１〜２０のアルキレン基を示し、Ｒ7は水素原子又は炭素数１〜３０の炭化水素基を示し、Ｘ１、Ｘ２、Ｘ３及びＸ４は同一でも異なっていてもよく、それぞれ酸素原子又は硫黄原子を示す。）

(In the formula (4), R4 and R5 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; R6 represents an alkylene group having 1 to 20 carbon atoms; A hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and X1, X2, X3 and X4 may be the same or different and each represents an oxygen atom or a sulfur atom.)

  Examples of the hydrocarbon group having 1 to 30 carbon atoms in R4 and R5 in the above formula (4) include an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

  Among the phosphorylated carboxylic acids, useful β-dithiophosphorylated propionic acid has a structure of the following formula (5).

  Specific examples of the β-dithiophosphorylated propionic acid include 3- (di-isobutoxy-thiophosphorylsulfanyl) -2-methyl-propionic acid.

The content of the phosphorus-containing carboxylic acid compound in the present lubricating oil composition is not particularly limited, but is preferably 0.001 to 1% by mass, more preferably 0.002 based on the total amount of the lubricating oil composition. It is -0.5 mass%.
If the content of the phosphorus-containing carboxylic acid compound is less than the lower limit, sufficient lubricity tends to be not obtained. On the other hand, even if it exceeds the upper limit, there is a tendency that the lubricity improvement effect corresponding to the content does not tend to be obtained, and furthermore, there is a possibility that the heat / oxidation stability and the hydrolysis stability may be lowered.

  In addition, about content of the compound whose R7 is a hydrogen atom among the phosphorylated carboxylic acid represented by the said Formula (4), Preferably it is 0.001-0.1 mass%, More preferably, it is 0.002-. It is 0.08 mass%, More preferably, it is 0.003-0.07 mass%, More preferably, it is 0.004-0.06 mass%, Most preferably, it is 0.005-0.05 mass%.

  Specific examples of the acidic phosphate ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monounol. Decyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid dibutyl phosphate Acid phosphate, dipentyl acid phosphate , Dihexyl acid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate phosphate, ditetradecyl acid phosphate decyl phosphate phosphate , Dihexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, and dioleyl acid phosphate.

  Examples of the amine salt of the acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. , Salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, and trioctylamine It is done.

  Examples of the phosphites include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, geode Rail phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl Examples thereof include phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, and tricresyl phosphite.

  Specific examples of the phosphorothionate include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphate. Phorothionate, tridecyl phosphorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, tri Hexadecyl phosphorothioate, triheptadecyl phosphorothionate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothioate , Trixylenyl phosphorothionate, cresyl diphenyl phosphorothionate, xylenyl diphenyl phosphorothionate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phosphorothionate, tris (N-Butylphenyl) phosphorothionate, Tris (isobutylphenyl) phosphorothionate, Tris (s-butylphenyl) phosphorothionate, Tris (t-butylphenyl) phosphorothionate, and the like can be given. Mixtures of these can also be used.

  Examples of the above-mentioned thiophosphate ester derivatives include esters and metal salts. Specifically, as the thiophosphate ester compounds, aliphatic thiophosphate esters such as triisopropyl thiophosphate, tributyl thiophosphate, ethyl dibutyl thiophosphate, Trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearyl thiophosphate, trioleyl thiophosphate; and aromatic thiophosphates such as benzylphenyl thiophosphate, allyl diphenyl thiophosphate, triphenyl thiophosphate , Tricresyl thiophosphate, ethyl diphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl thio Sulfate, ethyl phenyl diphenyl thiophosphate, diethyl phenyl phenyl thiophosphate, propyl phenyl diphenyl thiophosphate, dipropyl phenyl phenyl thiophosphate, triethyl phenyl thiophosphate, tripropyl phenyl thiophosphate, butyl phenyl diphenyl thiophosphate, dibutyl phenyl phenyl thiophosphate, Mention may be made of tributylphenylthiophosphate.

Specific examples of the metal thiophosphate include zinc dithiophosphate and molybdenum dithiophosphate. Examples of the zinc dithiophosphate generally include zinc dialkyldithiophosphate, zinc diaryldithiophosphate, and zinc arylalkyldithiophosphate. For example, the zinc group of zinc dialkyldithiophosphate is a zinc dialkyldithiophosphate having an alkylaryl group substituted with a primary or secondary alkyl group having 3 to 22 carbon atoms or an alkyl group having 3 to 18 carbon atoms. used.
Specific examples of zinc dialkyldithiophosphate include zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc dihexyldithiophosphate, zinc diisopentyldithiophosphate, zinc diethylhexyldithiophosphate, zinc dioctyldithiophosphate, Zinc nonyldithiophosphate, zinc didecyldithiophosphate, zinc didodecyldithiophosphate, zinc dipropylphenyldithiophosphate, zinc dipentylphenyldithiophosphate, zinc dipropylmethylphenyldithiophosphate, zinc dinonylphenyldithiophosphate, didodecylphenyldithiophosphate Zinc and the like.

Examples of the molybdenum dithiophosphate generally include molybdenum dialkyldithiophosphate, molybdenum diaryldithiophosphate, molybdenum arylalkyldithiophosphate, and the like. For example, the alkyl group of molybdenum dialkyldithiophosphate is a molybdenum dialkyldithiophosphate having an alkylaryl group substituted with a primary or secondary alkyl group having 3 to 22 carbon atoms or an alkyl group having 3 to 18 carbon atoms. used.
Specific examples of molybdenum dialkyldithiophosphates include molybdenum dipropyldithiophosphate, molybdenum dibutyldithiophosphate, molybdenum dipentyldithiophosphate, molybdenum dihexyldithiophosphate, molybdenum diisopentyldithiophosphate, molybdenum diethylhexyldithiophosphate, molybdenum dioctyldithiophosphate, Nonyldithiophosphate molybdenum, didecyldithiophosphate molybdenum, molybdenum dododecyldithiophosphate, dipropylphenyldithiophosphate molybdenum, dipentylphenyldithiophosphate molybdenum, dipropylmethylphenyldithiophosphate molybdenum, dinonylphenyldithiophosphate molybdenum, didodecylphenyldithiophosphate And molybdenum.

Examples of the thiocarbamic acid derivative include esters and metal salts, and specific examples include dithiocarbamic acid esters and dithiocarbamic acid metal salts.
Specific examples of dithiocarbamate esters include methyldibutyldithiocarbamate, ethyldipropyldithiocarbamate, decyldibutyldithiocarbamate, hexyldidecyldithiocarbamate, octadecyldiisopropyldithiocarbamate, octylmethylpropyldithiocarbamate, and isobutylpropyl-decyldithiocarbamate. Can be mentioned.

  Among the above metal salts of dithiocarbamate, zinc or molybdenum is particularly useful. Specific examples of molybdenum dialkyldithiocarbamate include, for example, molybdenum dibutyldithiocarbamate, sulfurized dipentyldithiocarbamate, sulfurized dihexyldithiocarbamate, sulfurized diheptyldithiocarbamate, sulfide dioctyldithiocarbamate, sulfide dinonyldithiocarbamate, Molybdenum didecyldithiocarbamate sulfide, molybdenum dididecyldithiocarbamate sulfide, molybdenum didodecyldithiocarbamate, molybdenum ditridecyldithiocarbamate, oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dipentyldithiocarbamate, oxymolybdenum dihexyldithiocarbamate, diheptyldithio Kalbami Oxymolybdenum oxysulfide, dioctyl dithiocarbamate oxymolybdenum sulfide, dinonyl dithiocarbamate oxymolybdenum sulfide, didecyldithiocarbamate oxysulfide oxymolybdenum, diundecyldithiocarbamate oxysulfide oxymolybdenum, didodecyldithiocarbamate oxymolybdenum sulfide, and ditridecyldithiocarbamate oxysulfide Examples thereof include oxymolybdenum.

  In addition to the above-described components, various additives can be appropriately used as necessary in order to further improve the performance. These include antioxidants, metal deactivators, extreme pressure agents, oiliness improvers, antifoaming agents, viscosity index improvers, pour point depressants, cleaning dispersants, rust inhibitors, demulsifiers, etc. And known lubricating oil additives.

  As the antioxidant used in the present invention, those used for lubricating oils are practically preferable, and amine-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants are exemplified. be able to. These antioxidants can be used singly or in combination within a range of 0.01 to 5% by mass with respect to 100% by mass of the base oil.

  Examples of the amine antioxidant include p, p′-dioctyl-diphenylamine (Seiko Chemical Co., Ltd .: Nonflex OD-3), p, p′-di-α-methylbenzyl-diphenylamine, and Np-butylphenyl. Dialkyl-diphenylamines such as -Np'-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and monooctyldiphenylamine, di (2,4-diethylphenyl) amine, di (2-ethyl- Bis (dialkylphenyl) amines such as 4-nonylphenyl) amine, alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine, Nt-dodecylphenyl-1-naphthylamine, 1-naphthylamine, phenyl-1 -Naphthylamine, phenyl Aryl-naphthylamines such as 2-naphthylamine, N-hexylphenyl-2-naphthylamine, N-octylphenyl-2-naphthylamine, N, N′-diisopropyl-p-phenylenediamine, N, N′-diphenyl-p-phenylene Examples include phenylenediamines such as diamine, phenothiazines (manufactured by Hodogaya Chemical Co., Ltd .: Phenothiazine), and phenothiazines such as 3,7-dioctylphenothiazine.

  Examples of sulfur-based antioxidants include dialkyl sulfides such as didodecyl sulfide and dioctadecyl sulfide, didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, and dodecyl octadecyl thiodipropionate. Examples include thiodipropionic acid esters and 2-mercaptobenzimidazole.

Examples of phenolic antioxidants include 2-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4- Dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (manufactured by Kawaguchi Chemical Co., Ltd .: Antage DBH), 2,6-di-t-butylphenol such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol 2,6-di-t-butyl- such as -4-alkylphenols, 2,6-di-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-4-ethoxyphenol - there is a alkoxy phenols.
3,5-di-t-butyl-4-hydroxybenzyl mercapto-octyl acetate, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) Yoshinox SS), n-dodecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2'-ethylhexyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, alkyl such as benzenepropanoic acid 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-carbon number 7 to carbon number 9 side chain alkyl ester (Ciba Specialty Chemicals: Irganox L135) -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionates, 2,6-di-tert-butyl Ru-α-dimethylamino-p-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd .: Antage W-400), 2,2′-methylenebis (4-ethyl) There are 2,2′-methylenebis (4-alkyl-6-t-butylphenol) s such as (−6-t-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd .: Antage W-500).
Further, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd .: Antage W-300), 4,4′-methylenebis (2,6-di-tert-butylphenol) (shell) -Japan company make: Ionox220AH), 4,4'-bis (2,6-di-t-butylphenol), 2, 2- (di-p-hydroxyphenyl) propane (shell Japan company make: bisphenol A), 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 4,4′-cyclohexylidenebis (2,6-t-butylphenol), hexamethylene glycol bis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals: Irganox L109), triethyl Renglycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (manufactured by Yoshitomi Pharmaceutical: Tominox 917), 2,2′-thio- [diethyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals: Irganox L115), 3,9-bis {1,1-dimethyl-2- [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionyloxy] ethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane (Sumitomo Chemical: Sumilizer GA80), 4,4'-thiobis (3-methyl -6-t-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd .: Antage RC), bis such as 2,2′-thiobis (4,6-di-t-butyl-resorcin) There is a phenol compound.
Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (manufactured by Ciba Specialty Chemicals: Irganox L101), 1,1,3-tris (2-methyl) -4-hydroxy-5-t-butylphenyl) butane (Yoshitomi Pharmaceutical Co., Ltd .: Yoshinox 930), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene (manufactured by Shell Japan: Ionox 330), bis- [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 2- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) methyl-4- (2 ", 4" -di-tert-butyl-3 "-hydroxyphenyl) methyl Of polyphenols such as -6-tert-butylphenol, 2,6-bis (2'-hydroxy-3'-tert-butyl-5'-methyl-benzyl) -4-methylphenol, pt-butylphenol and formaldehyde Examples include condensates and phenol aldehyde condensates such as a condensate of pt-butylphenol and acetaldehyde.

  Examples of phosphorus antioxidants include triaryl phosphites such as triphenyl phosphite and tricresyl phosphite, trialkyl phosphites such as trioctadecyl phosphite and tridecyl phosphite, and tridodecyl trithiophosphite. It is done.

Metal deactivators that can be used in conjunction with the compositions of the present invention include 4-alkyl-benzotriazoles such as benzotriazole, 4-methyl-benzotriazole, 4-ethyl-benzotriazole, 5-methyl-benzotriazole, 5- 5-alkyl-benzotriazoles such as ethyl-benzotriazole, 1-alkyl-benzotriazoles such as 1-dioctylaminomethyl-2,3-benzotriazole, 1 such as 1-dioctylaminomethyl-2,3-toltriazole -2- (alkyldithio) such as benzotriazole derivatives such as alkyl-tolutriazoles, benzimidazole, 2- (octyldithio) -benzimidazole, 2- (decyldithio) -benzimidazole, 2- (dodecyldithio) -benzimidazole ) Benzimidazole derivatives such as 2- (alkyldithio) -toluimidazoles such as benzimidazoles, 2- (octyldithio) -toluimidazole, 2- (decyldithio) -toluimidazole, 2- (dodecyldithio) -toluimidazole, etc. is there.
Indazole derivatives such as tolindazoles such as indazole, 4-alkyl-indazole, 5-alkyl-indazole, benzothiazole, 2-mercaptobenzothiazole derivative (manufactured by Chiyoda Chemical Co., Ltd .: Thiolite B-3100), 2- (hexyl) 2- (Alkyldithio) benzothiazoles such as dithio) benzothiazole, 2- (octyldithio) benzothiazole, 2- (alkyldithio) such as 2- (hexyldithio) tolthiazole, 2- (octyldithio) tolthiazole Tolthiazoles, 2- (N, N-diethyldithiocarbamyl) benzothiazole, 2- (N, N-dibutyldithiocarbamyl) -benzothiazole, 2- (N, N-dihexyldithiocarbamyl) -benzothiazole 2- (N, N-dia Kirdithiocarbamyl) benzothiazoles, 2- (N, N-diethyldithiocarbamyl) tolthiazole, 2- (N, N-dibutyldithiocarbamyl) tolthiazole, 2- (N, N-dihexyldithiocarbamyl) ) There are benzothiazole derivatives such as 2- (N, N-dialkyldithiocarbamyl) -torzothiazoles such as tolthiazole.
Furthermore, 2- (alkyldithio) -benzoxazoles such as 2- (octyldithio) benzoxazole, 2- (decyldithio) benzoxazole, 2- (dodecyldithio) benzoxazole, 2- (octyldithio) toluoxazole, 2 Benzoxazole derivatives such as 2- (alkyldithio) toluazoles such as-(decyldithio) toluxazole and 2- (dodecyldithio) toluxazole, 2,5-bis (heptyldithio) -1,3,4-thiadiazole, 2 , 5-bis (nonyldithio) -1,3,4-thiadiazole, 2,5-bis (dodecyldithio) -1,3,4-thiadiazole, 2,5-bis (octadecyldithio) -1,3,4 2,5-bis (alkyldithio) -1,3,4-thio such as thiadiazole Diazoles, 2,5-bis (N, N-diethyldithiocarbamyl) -1,3,4-thiadiazole, 2,5-bis (N, N-dibutyldithiocarbamyl) -1,3,4-thiadiazole 2,5-bis (N, N-dialkyldithiocarbamyl) -1,3,4-thiadiazoles such as 2,5-bis (N, N-dioctyldithiocarbamyl) -1,3,4-thiadiazole 2-N, N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole, 2-N, N-dioctyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole Thiadiazole derivatives such as N, N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazoles, 1-di-octylaminomethyl-2,4-triazol Like 1-alkyl-2,4-triazole derivative of triazoles such like.
These metal deactivators can be used singly or in combination within a range of 0.01 to 0.5% by mass with respect to 100% by mass of the base oil.

For the purpose of improving oiliness, a fatty acid ester of a polyhydric alcohol can be blended with the lubricating oil composition of the present invention. For example, a partial or complete ester of a saturated or unsaturated fatty acid having 1 to 24 carbon atoms of a polyhydric alcohol such as glycerol, sorbitol, alkylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, and xylitol can be used.
Examples of glycerol esters include glycerol monolaurate, glycerol monostearate, glycerol monopalmitate, glycerol monooleate, glycerol dilaurate, glycerol distearate, glycerol dipalmitate, glycerol diolate, and the like.
The sorbitol esters include sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol dilaurate, sorbitol dipalmitate, sorbitol distearate, sorbitol diolate, sorbitol tristearate, sorbitol tris Examples include laurylate, sorbitol trioleate, and sorbitol tetraoleate.
Examples of alkylene glycol esters include ethylene glycol monolaurate, ethylene glycol monostearate, ethylene glycol monooleate, ethylene glycol dilaurate, ethylene glycol distearate, ethylene glycol diolate, propylene glycol monolaurate, propylene glycol monostearate. Rate, propylene glycol monooleate, propylene glycol dilaurate, propylene glycol distearate, propylene glycol dioleate and the like.
Examples of neopentyl glycol esters include neopentyl glycol monolaurate, neopentyl glycol monostearate, neopentyl glycol monooleate, neopentyl glycol dilaurate, neopentyl glycol distearate, neopentyl glycol dioleate, and the like. .
Examples of trimethylolpropane esters include trimethylolpropane monolaurate, trimethylolpropane monostearate, trimethylolpropane monooleate, trimethylolpropane dilaurate, trimethylolpropane distearate, trimethylolpropanediolate, pentaerythritol monoester. There is laurate etc.
Examples of the pentaerythritol ester include pentaerythritol monostearate, pentaerythritol monooleate, pentaerythritol dilaurate, pentaerythritol distearate, pentaerythritol dioleate, dipentaerythritol monooleate, and the like.
As such a fatty acid ester of a polyhydric alcohol, a partial ester of a polyhydric alcohol and an unsaturated fatty acid is preferably used.

In order to improve low temperature fluidity and viscosity characteristics, a pour point depressant and a viscosity index improver may be added to the lubricating oil composition of the present invention.
Examples of the viscosity index improver include non-dispersed viscosity index improvers such as polymethacrylates, ethylene-propylene copolymers, styrene-diene copolymers, polyisobutylene, polystyrene and other olefin polymers, and nitrogen-containing compounds. Examples thereof include a dispersion type viscosity index improver obtained by copolymerizing monomers. The addition amount can be used in the range of 0.05 to 20% by mass with respect to 100% by mass of the base oil.
Examples of the pour point depressant include polymethacrylate polymers. The addition amount can be used in the range of 0.01 to 5% by mass with respect to 100% by mass of the base oil.

  In order to impart antifoaming properties to the lubricating oil composition of the present invention, an antifoaming agent may be added. Antifoaming agents suitable for the present invention include known ones that are commonly used as lubricating oil additives. Examples thereof include organosilicates such as dimethylpolysiloxane, diethyl silicate and fluorosilicone, and non-silicone antifoaming agents such as polyalkyl acrylate. The addition amount can be used alone or in combination within a range of 0.0001 to 0.1% by mass with respect to 100% by mass of the base oil.

  Demulsifiers suitable for the present invention include those commonly used as lubricating oil additives. The addition amount can be used in the range of 0.0005 to 0.5 mass% with respect to 100 mass% of the base oil.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

In the preparation of Examples 1 to 17 and Comparative Examples 1 to 4, the following base oils and additives were prepared.
(1) Base oil A: Synthetic base oil / PAO (poly α-olefin) (characteristic: kinematic viscosity at 100 ° C .; 6.36 mm ² / s, viscosity index; 136, total sulfur content (sulfur element equivalent value); 5 mass (below ppm)
(2) Base oil B: Group 1 paraffinic mineral oil; paraffin obtained by applying a suitable combination of refining means such as solvent dewaxing to lubricating oil fractions obtained by distillation of crude oil under reduced pressure HVI60 (registered trademark) and HVI160S (registered trademark), which are base mineral oils, adjusted to ISO VG # 32 (characteristics: kinematic viscosity at 100 ° C .; 5.45 mm ² / s, viscosity index: 104, all Sulfur content (sulfur element conversion value); 0.5 mass% = 5000 mass ppm)
(3) Base oil C: GTL (gas-tri-liquid) base oil synthesized by the Fischer-Tropsch method, which is a natural gas liquid fuel technology, and adjusted in viscosity to ISO VG # 32 (characteristic: 100 ° C. Kinematic viscosity; 6.25 mm ² / s, viscosity index: 145, total sulfur content (sulfur element equivalent); less than 10 ppm by mass)

(4) Additive A1: Polyalkylene polyamide (manufactured by Chevron: Oloa 340D)
(5) Additive A2: Oleyl sarcosine (Ciba Specialty Chemicals: Sarkosyl O)
(6) Additive A3: Aspartic acid derivative (King: K-corr100)
(7) Additive A4: Synthetic Ca sulfonate (manufactured by Infineum: Infineum)
9330)
(8) Additive A5: Alkenyl succinate (manufactured by Lubrizol: Lubrizol)
859)
The additives A1 to A5 mainly act as a rust preventive agent.

(9) Additive B1: β-dithiophosphorylated propionic acid (manufactured by Ciba Specialty Chemicals: Irgalube 353)
(10) Additive B2: Octyl Acid Phosphate (11) Additive B3: Zinc Dialkyldithiophosphate (ZnDTP / Lubrisol: Lubrizol 1095)
(12) Additive B4: Zinc dialkyldithiophosphate (ZnDTP / Lubrisol: Lubrizol 1375)
(13) Additive B5: Molybdenum dialkyldithiophosphate (MoDTP / MolvanL manufactured by Vanderbilt)
(14) Additive B6: Molybdenum dialkyldithiocarbamate (MoDTC / Adeka Sakura Lube 165)
(15) Additive B7: Molybdenum dialkyldithiocarbamate (MoDTC / Ketjen OX77M)
The additives B1 to B7 mainly function as a friction modifier.

(16) Additive C1: Alkylated diphenylamine (Ciba Specialty Chemicals: Irganox L57)
(17) Additive C2: Phenolic antioxidant (Ciba Specialty Chemicals: Irganox L135)
The additives C1 and C2 mainly function as an antioxidant.

  Lubricating oil compositions of Examples 1 to 17 having the compositions shown in Tables 1 to 4 and Comparative Examples 1 to 4 shown in Table 5 were prepared using the above base oils and additives. Further, as Comparative Example 5, a commercial machine tool lubricant was prepared. In addition, the quantity of each composition component in Tables 1-5 was displayed by the mass%.

(Measurement of characteristic values)
In order to know the characteristics of the lubricating oil compositions of Examples 1 to 17 and Comparative Examples 1 to 5, the kinematic viscosity at 40 ° C. (based on JIS K2283) and the kinematic viscosity at 100 ° C. (based on JIS K2283) , Viscosity index (based on JIS K2283), and acid value (based on JIS K2501) were measured.
Each measurement result was described in Tables 1-5.

(test)
Using the lubricating oil compositions of Examples 1 to 17 and Comparative Examples 1 to 5, the following tests were performed to see the performance.

(Rust prevention test)
Based on JIS K2510, 300 ml of sample oil is collected in a container installed in a thermostat and stirred at 1000 revolutions per minute. When the temperature reaches 60 ° C., an iron test piece is inserted into the sample oil, 30 ml of artificial seawater is further added, and stirring is continued for 24 hours while maintaining the temperature at 60 ° C., after which the test piece is taken out and the test piece is rusted. The state of occurrence was evaluated visually.
The evaluation criteria were as follows.
No rust; no rust generation (0%)
Minor: 6 or less point rusts of 1 mm or less Medium; Exceeding the above-mentioned minor, less than 5% of the surface area; Exceeding the above-mentioned moderate;

(Ceramic lubricity test)
The shell 4 ball wear test was performed by the test method standardized by ASTM D 4172, and the lubricity of each lubricating oil composition was evaluated. Conventional shell 4-ball wear test, but the test conditions are performed in 1200 m ^-1 to a relatively low speed and 1800 m ^-1 (slip velocity), in view of the actual use conditions, more severe following test conditions The oil temperature rise rate, the maximum torque, the friction coefficient, and the wear scar diameter of the fixed ball were used as indices for evaluating the lubricating performance.
<Test conditions>
Test ball: The rotating ball was made of ceramics (Si ₃ N ₄ ), and the fixed ball was made of bearing steel (SUJ-2).
Load (P): 40.0 kgf (= 392N)
Rotational speed: 6,000m ^-1
Test time: 30 minutes Temperature: Room temperature (at start of test)
Measurement: From the start to the end of the test, the friction torque (coefficient of friction), test oil temperature, and room temperature are automatically measured, and the oil temperature rise rate (° C / 10 s), maximum torque (kgf · cm), and coefficient of friction are calculated. It calculated | required by the following formula. Moreover, the wear scar diameter of SUJ-2 ball | bowl (fixed sphere) was measured after completion | finish of a test.
Friction coefficient = T / (0.4488 × P)
[T: friction torque (kgf · cm), P: load (kgf)]
1 kgf = 9.80665 N, and 1 kgf · cm = 9.80665 N · cm.

<Score of measurement results>
(1) About wear scar diameter ◎: Less than 0.7 ○: 0.7 or more and less than 1.0 ×: 1.0 or more (2) About oil temperature rise rate ◎: Less than 0.15 ○: 0.15 or more and 0 Less than 2 ×: 0.2 or more (3) Maximum torque ◎: Less than 1.8 ○: 1.8 or more and less than 2.7 ×: 2.7 or more (4) Friction coefficient ◎: Less than 0.100 ○ : 0.100 or more and less than 0.150 ×: 0.150 or more

(Test results)
Each test result is shown in Tables 1-5.

(Evaluation)
When the base oil A (PAO) of Example 1 is blended with the polyalkylene polyamide of the additive A1, no rust is observed, and the result in the shell four-ball wear test is also good. Moreover, in the thing of Example 2 which added the antioxidant of additive C1, C2 to Example 1, the wear scar diameter is small. In place of the additive A1 of Example 2, Example 3 using oleyl sarcosine acid of Additive A2 and Example 4 using an aspartic acid derivative of Additive A3 also showed no occurrence of rust. The results in the shell four-ball wear test are also good.
In Examples 5, 6, and 7 in which β-dithiophosphorylated propionic acid as additive B1 was added to those shown in Examples 2, 3, and 4 above, no rust was observed and shell 4 ball wear was observed. The result in the test is also good, and the wear scar diameter is small.
In Examples 8 and 9, the base oil A of Example 5 was changed to the base oil B group 1 paraffinic mineral oil and the base oil C GTL base oil. The result is obtained.
In Example 10, octyl acid phosphate of additive B2 was used instead of additive B1 of Example 5, and this can also be used as a lubricating oil composition.
In Examples 11 and 12, the additive A1 + A2 and the additive A1 + A3 were used in combination with the additive A1 instead of the additive A1 of Example 10, and a better result than that of Example 10 was obtained. .
In Examples 13 to 17, instead of the octyl acid phosphate of additive B2 of Example 10, zinc dialkyldithiophosphate of additive B3, zinc dialkyldithiophosphate of additive B4, and dialkyldithiophosphoric acid of additive B5 Molybdenum, molybdenum dialkyldithiocarbamate of additive B6, and molybdenum dialkyldithiocarbamate of additive B7 are used, and these can also be suitably used as a lubricating oil composition.
Among the above examples, those suitable as the lubricating oil composition for ceramic ball rolling bearings are those shown in Examples 5 to 12.
On the other hand, in the base oil A of Comparative Example 1, a high degree of rust was generated in the rust prevention test, and in the shell four-ball wear test, the oil temperature rising speed, the maximum torque, the friction coefficient were large, and the wear scar diameter was large. Bad results are coming out. In the case of adding the alkylated diphenylamine of the additive C1 and the phenolic antioxidant of the additive C2 to the base oil A of Comparative Example 2, good results were obtained in the shell 4-ball wear test, but in the rust prevention test High degree of rust has occurred. In the case of using the synthetic Ca sulfonate of additive A4 of Comparative Example 3 and the additive C1 + C2, rust is not generated in the rust prevention test, but the result in the shell 4-ball wear test is poor. Further, this shell four-ball wear test should be conducted for 1800 seconds, but smoke was emitted in 430 seconds and there was a risk of fire, so the test was stopped. In the case of using the alkenyl succinic acid ester of additive A5 of Comparative Example 4 and the additive C1 + C2, rust is not generated in the rust prevention test, but the result in the shell four-ball wear test is bad. Further, in the commercially available lubricating oil for machine tools of Comparative Example 5, the generation of rust was not observed, but the result in the shell 4-ball wear test was bad.
Thus, none of the comparative examples meet the requirements for ceramic ball rolling bearing lubricants, and may not be suitable for use as oil-air lubricants for high-speed spindles that use ceramic ball rolling bearings. understood.

Claims (10)

At least one base oil selected from mineral oil and / or synthetic oil is selected from the group of acid amides, sarcosine acids, or aspartic acid derivatives obtained by reacting amines with saturated monocarboxylic acids having 12 to 30 carbon atoms A lubricating oil composition for a ceramic ball rolling bearing , comprising 0.01 to 5% by mass of at least one additive. The lubricating oil composition for a ceramic ball rolling bearing according to claim 1, wherein the amine of the acid amide is a polyalkylamine. Phosphorus-containing carboxylic acid, phosphorus-containing carboxylic acid ester, acidic phosphate ester, amine salt of acidic phosphate ester, phosphite ester, phosphorothionate, thiophosphate ester, metal salt of thiophosphate, thiocarbamate ester, or thio The lubricating oil composition for a ceramic ball rolling bearing according to claim 1 or 2, further comprising at least one of metal salts of carbamic acid. The lubricating oil composition for a ceramic ball rolling bearing according to claim 3, wherein the phosphorus-containing carboxylic acid or phosphorus-containing carboxylic acid ester is β-dithiophosphorylated propionic acid or β-dithiophosphorylated propionic acid ester. The lubricating oil composition for a ceramic ball rolling bearing according to claim 3, wherein the metal salt of thiophosphate is zinc dialkyldithiophosphate or molybdenum dialkyldithiophosphate. 4. The lubricating oil composition for a ceramic ball rolling bearing according to claim 3, wherein the metal salt of thiocarbamic acid is zinc dithiocarbamate or molybdenum dithiocarbamate. The lubricating oil composition for a ceramic ball rolling bearing according to any one of claims 1 to 6, further comprising an aromatic amine compound and a phenol compound in the lubricating oil composition. The lubricating oil composition for a ceramic ball rolling bearing according to any one of claims 1 to 7, wherein the base oil is a synthetic oil. The lubricating oil composition for a ceramic ball rolling bearing according to claim 8, wherein the synthetic oil is a poly-α-olefin. The lubricating oil composition for a ceramic ball rolling bearing according to claim 8, wherein the synthetic oil is GTL.