JP5525149B2 - Lubricant composition - Google Patents

Description

  The present invention relates to an improvement of a lubricant composition, and more particularly to a lubricant composition excellent in heat resistance and load resistance.

Conventional lubricant compositions such as greases that require heat resistance and load resistance include lithium soap grease compositions obtained by adding a lithium salt of a fatty acid to mineral oil or synthetic oil (Patent Document 1), and aluminum complex soaps. A grease composition or a urea grease composition (Patent Document 2) in which an isocyanate and an amine are reacted in a mineral oil or a synthetic oil to form a urea compound has been used.
In addition, in order to improve heat resistance, it has been proposed to obtain a urea grease composition using a urea compound having a fluorine atom in the molecular skeleton (Patent Document 3), which has a special structure. The disadvantage is that it is generally difficult to obtain.

  Furthermore, a fluorine-based grease composition in which perfluoropolyether of fluorine oil is used as a base oil and is increased with a fluorine resin is known as a heat-resistant product (Patent Document 4). Such a fluorine-based grease composition is lubricated at a high temperature exceeding 150 ° C., lubricated at a site in contact with a chemical, lubricated under a high vacuum, lubricated under radiation irradiation, and durability in various precision instruments. It is also used in lubricated parts where stability is required.

However, in the above-mentioned fluorine-based grease composition, the fluororesin is heated and dissolved in a fluorine solvent at the time of production, and this is dispersed in the fluorine oil of the base oil, and further, the fluorine solvent is removed from the generated grease composition. In addition, since it is necessary to perform processing with a decompression device, there is a disadvantage that the manufacturing cost is high.
In addition, since the above-mentioned fluororesin and the fluorine solvent for dissolving it are also expensive, the price of the fluorine-based grease composition is further increased. It was limited.
Japanese Patent Laid-Open No. 5-86392 JP-A-6-330072 JP-A-11-611169 JP 2007-154084 A

The present invention provides a fluorine-based lubricant composition that is safe and easy to obtain without using a fluororesin or a fluorine solvent that dissolves the fluororesin, and is excellent in heat resistance and load resistance at low cost. A fluorine-based lubricant composition having high performance is provided.
Fluorine grease is excellent in heat resistance and oxidation stability, but has insoluble properties in most organic solvents and oils. For this reason, it does not fit well with various additives, and depending on the lubricating material and use conditions, wear is often accelerated and rust is often generated.
The present invention provides a fluorine-based lubricant composition that reduces friction coefficient and improves wear resistance under severe lubrication conditions.
The present invention also provides a fluorine-based lubricant composition excellent in rust prevention performance.

The present inventors have found that when tricalcium phosphate is added to fluorine oil, an extremely excellent thickening effect is exhibited, and this tricalcium phosphate has some other thickening effects. The present invention has been completed based on the fact that the fluorine-based lubricant composition prepared in combination is excellent in heat resistance and load resistance and can maintain its performance for a long time even at high temperatures.
That is, the present invention further has a thickening action of fluorine oil containing at least one of perfluoropolyether or fluorosilicone , 1 to 40% by mass of tribasic calcium phosphate as a thickener, based on the total composition. Fluorine-based by containing at least one of urea compound, alkali metal soap, alkali metal composite soap, alkali metal sulfonate, alkaline earth metal sulfonate, aluminum soap, aluminum composite soap, terephthalamate metal salt, clay and silica airgel This lubricant composition is used.

According to the present invention, it is possible to obtain a lubricant composition that is excellent in heat resistance and load resistance and has a long life at high temperatures. Further, tricalcium phosphate is more economical than fluororesin and a fluorine solvent in which it is dissolved, and a lubricant composition advantageous in terms of cost can be obtained safely and easily. When tricalcium phosphate is used, the raw material is inexpensive and the consistency yield is good as compared with general fluorine grease. That is, a lubricant having a desired hardness can be obtained with a small amount of thickener.
Naturally, the lubricant composition of the present invention can be used for machines, bearings, and the like that are generally used, and exhibits excellent performance under lubricating conditions that require more severe high temperature properties.
For example, in automobiles, the engine periphery of starters, alternators and various actuators, propeller shafts, constant velocity joints (CVJ), power trains such as wheel bearings and clutches, electric power steering (EPS), braking devices, ball joints, door hinges And various parts such as a handle part and a cooling fan motor are suitable for these applications.
Furthermore, it is also suitable for various high-temperature places such as construction machines such as power shovels, bulldozers, crane cars, steel, paper industry, forestry, agricultural machinery, chemical plants, drying furnaces, and copying machines.
Other applications include hard disk bearings, plastic lubrication, cartridge grease, etc., which are also suitable for these applications.

  As the fluoro oil, perfluoropolyether, fluorosilicone, and the like can be used, and at least one of these can be used, and can be used by appropriately mixing them.

Examples of such fluorine oils include perfluoropolyether and derivatives thereof, fluorosilicone, chlorotrifluoroethylene, fluorophosphazene, and the like, and mixed oils thereof.
The kind of perfluoropolyether is not particularly limited, and is preferably composed of at least one selected from the following fluorooxyalkylene structural units.
X in the following formulas 6 and 7 is “CF ₃ (CF ₂ ) _n —”, and n is an integer of 0 to 4.

(Chemical formula 1)
_{- (- CF 2 CF 2 O} -) - (1)
(Chemical formula 2)
_{- (- CF 2 O -)} - (2)
(Chemical formula 3)
_{- (- CF 2 CF (CF} 3) O -) - (3)
(Chemical formula 4)
_{- (- CF (CF 3)} O -) - (4)
(Chemical formula 5)
_{- (- CF 2 CF 2 CF} 2 O -) - (5)
(Chemical formula 6)
_{- (- CF 2 CF (OX} ) O -) - (6)
(Chemical formula 7)
-(-CF (OX) O-)-(7)

When the perfluoropolyether is composed of two or more of the above fluorooxyalkylene structural units, each structural unit is statistically distributed along the chain. Then, the terminal _{group, CF 3 -, C 2 F} 5 -, C 3 F 7 -, CF 2 Cl (CF 3) CF-, CF 3 CFClCF 2 -, CF 2 ClCF 2 -, CF 2 Cl-, A fluoroalkyl group optionally having one H and / or Cl, such as CHF ₂ —, CF ₃ CHF—, and the like.

The fluorosilicone of the present invention is not particularly limited as long as it is a fluorosilicone having a substituent containing a fluorine atom and has a viscosity in a range that can be used as a base oil of a lubricant composition. .
Specific examples of fluorosilicone that can be suitably used include, for example, those represented by the following formula (8), but are not limited thereto.
Furthermore, other known lubricant compositions can be added to such perfluoropolyethers and fluorosilicones as long as they do not interfere with the intended purpose of the present invention.

(Chemical Formula 8)

In the above formula 8, R ¹ is a hydrocarbon group having 1 to 3 carbon atoms, R ² is a methyl group, an ethyl group, a vinyl group, a phenyl group or a —CH ₂ CH ₂ R group (R: a carbon number of 1 10 perfluoroalkyl group), and at least 50% of the R ² is a “—CH ₂ CH ₂ R group”. N is the number of ranges giving a usable viscosity range.

Tribasic calcium phosphate described above are, in general, in those having a chemical structure of the hydroxyapatite composition represented by _[Ca 3 _{(PO 4) 2] 3 · Ca (OH) 2,} Ca 3 (PO ₄ ) What is represented by ₂ can also be used.
In the examples and the like described below in the present invention, [Ca ₃ (PO ₄ ) ₂ ] ₃ · Ca (OH) ₂ is used, and the content is also expressed in mass based on this.

A lubricant composition can be obtained by adding tribasic calcium phosphate to the fluorine oil and mixing and kneading them together, or by using the other thickener together . As the amount of tricalcium phosphate added increases, the consistency of the lubricant composition increases and gradually becomes a grease state.
When obtaining a grease-like lubricant composition, the amount of tricalcium phosphate used is about 1 to 40% by weight, preferably about 5 to 20% by weight, more preferably based on the total amount of the lubricant composition. About 7 to 15% by mass is preferably blended.
When the blending amount of tribasic calcium phosphate is less than 1% by mass, it does not become a state normally referred to as a grease, but an increase in consistency is seen, so it is used for an application suitable for the obtained state. be able to. In addition, when it exceeds 40% by mass, the lubricant composition becomes hard and does not become a smooth butter shape, so it is considered that it is not suitable for grease, but it can be used for appropriate applications according to the state. .

In addition to the above components, the lubricant composition of the present invention may be appropriately combined with a rust inhibitor, anticorrosive agent, antioxidant, extreme pressure agent, antiwear agent and other additives depending on the application. it can.
Examples of the rust inhibitor and anticorrosive agent include those commonly used. Organic acid derivatives, organic amine derivatives, sulfurized fatty acid derivatives, surfactants, dibasic acid salts, benzotriazole derivatives, benzothiazole derivatives, benzimidazole derivatives Thiocarbamate, among others, at least one selected from alkali metal dibasic acid salts, alkaline earth metal dibasic acid salts, benzotriazole derivatives, benzothiazole derivatives, benzimidazole derivatives, and thiocarbamates. It is good to use.

Among the organic acid derivatives, succinic acid derivatives are preferable.
The succinic acid derivative is represented by the following general formula (9).

In the above general formula 9, X ₁ and X ₂ are each hydrogen or the same or different alkyl group, alkenyl group or hydroxyalkyl group having 3 to 6 carbon atoms, preferably a hydrogen atom, 1-hydroxypropyl group, 2-hydroxypropyl group, 2-methylpropyl group, and tertiary butyl group. X ₃ is an alkyl group or alkenyl group having 1 to 30 carbon atoms, an alkyl group having an ether bond, or a hydroxyalkyl group. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, dodecylene, tridecyl, tetradecyl group, tetradecylene, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecylene, eicosyl group, docosyl group, an alkoxycarbonyl propyl, _{3- (C} 6 ~C ₁₈₎ hydrocarbonoxy _(C 3 _{~C 6)} alkyl group, alkoxy propyl, _{3- (C} 6 ~C ₁₈₎ hydrocarbonoxy _(C 3 _{~C 6)} alkyl group, more preferably, tetraisopropyl group, an oleyl group, cyclohexyloxy propyl group, 3-octyloxy propyl , 3-isooctyloxypropyl group 3-decyloxypropyl group, 3-isodecyloxypropyl group, and 3- (C ₁₂ -C ₁₆ ) alkoxypropyl group are preferable. Aminated products of these compounds may also be used.
The succinic acid derivative has an acid value defined by JIS K2501 of 10 to 300 mgKOH / g, preferably 30 to 200 mgKOH / g.

  Examples of the organic amine derivatives include diethanolamines, monoalkyl primary amines, monoalkenyl primary amines, alkyl diamine / di fatty acid salts, alkenyl diamine / di fatty acid salts, alkyl diamines, and alkenyl diamines.

Examples of the diethanolamines include those represented by the following general formula (10).
(Chemical Formula 10)
X ₁₀ -N- (X ₁₁ ) ₂ (10)

Among the above formula _{10, X 10} is an alkyl or alkenyl group having 1 to 30 carbon atoms, preferably carbon atoms of _{X 10} is 1 to 20, more preferably 1 to 8 or 12 to 18 is good. X ₁₁ is a hydroxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 or 12 to 18 carbon atoms in X ₁₁ .

  Examples of such diethanolamines include N-octyldiethanolamine, N-nonyldiethanolamine, N-decyldiethanolamine, N-undecyldiethanolamine, N-lauryldiethanolamine, N-tridecyldiethanolamine, N-myristyldiethanolamine, N-pentadecyldiethanolamine. N-palmityldiethanolamine, N-heptadecyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, N-isostearyldiethanolamine, N-nonadecyldiethanolamine, N-eicosyldiethanolamine, N-coconutdiethanolamine, N-tallow Diethanolamine, N-hydrogenated beef tallow diethanolamine, N-soybean diethanol N-alkyldiethanolamines such as min, N-octyldipropanolamine, N-nonyldipropanolamine, N-decyldipropanolamine, N-undecyldipropanolamine, N-lauryldipropanolamine, N-tridecyl Dipropanolamine, N-myristyldipropanolamine, N-pentadecyldipropanolamine, N-palmityldipropanolamine, N-heptadecyldipropanolamine, N-oleyldipropanolamine, N-stearyldipropanolamine, N -Isostearyl dipropanolamine, N-nonadecyl dipropanolamine, N-eicosyl dipropanolamine, N-coconut dipropanolamine, N-tallow dipropanolamine, N-hydrogenated tallow dip Panoruamin, there is N- alkyl dipropanolamine such as N- soybean dipropanolamine.

Examples of the monoalkyl primary amine and monoalkenyl primary amine include those represented by the following general formula (11).
(Chemical Formula 11)
H ₂ N-X ₁₂ (11)

Among the above formula _{11, X 12} is an alkyl group, an alkenyl group having 1 to 30 carbon atoms. For example, laurylamine, coconutamine, n-tridecylamine, myristylamine, n-pentadecylamine, n-palmitylamine, n-heptadecylamine, n-stearylamine, isostearylamine, n-nonadecylamine, n -Eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine, n-pentacosylamine, oleylamine, beef tallow amine, hydrogenated tallow amine, soybean amine and the like. X ₁₂ preferably has 8 to 24 carbon atoms, more preferably 12 to 18 carbon atoms. X ₁₂ may be linear aliphatic, branched aliphatic, or tertiary alkyl group.

Examples of the alkyl diamine / difatty acid salt and alkenyl diamine / di fatty acid salt include N-alkyl (C ₁₄ -C ₁₈ ) trimethylenediamine oleate (tallow diamine oleate), N-alkyl (C ₈ ). -C _{18)-1,3-diaminopropane-adipate} (here diamine adipate) and the like.

Examples of the alkyl diamine and alkenyl diamine include those represented by the following general formula (12).
(Chemical formula 12)
X ₁₃ -NH-X ₁₄ -NH ₂ (12)

In General Formula 12, X ₁₃ is an alkyl group or alkenyl group having 1 to 30 carbon atoms. X ₁₃ preferably has 8 to 24 carbon atoms, more preferably 12 to 18 carbon atoms. X ₁₄ is an alkylene group having 1 to 12 carbon atoms. X ₁₄ preferably has 1 to 8 carbon atoms, more preferably 2 to 4 carbon atoms.
As such, for example, N-octyl-1,2-ethylenediamine, N-nonyl-1,2-ethylenediamine, N-decyl-1,2-ethylenediamine, N-undecyl-1,2-ethylenediamine, N-lauryl- 1,2-ethylenediamine, N-tridecyl-1,2-ethylenediamine, N-myristyl-1,2-ethylenediamine, N-pentadecyl-1,2-ethylenediamine, N-palmityl-1,2-ethylenediamine, N-heptadecyl- 1,2-ethylenediamine, N-oleyl-1,2-ethylenediamine, N-stearyl-1,2-ethylenediamine, N-isostearyl-1,2-ethylenediamine, N-nonadecyl-1,2-ethylenediamine, N-eicosyl -1,2-ethylenediamine, N-coconut 1,2-ethylenediamine, N- tallow-1,2-ethylenediamine, N- hydrogenated tallow-1,2-ethylenediamine, N- soybean -1,2-ethylenediamine, is ethylenediamines equal.

  N-octyl-1,3-propylenediamine, N-nonyl-1,3-propylenediamine, N-decyl-1,3-propylenediamine, N-undecyl-1,3-propylenediamine, N-lauryl- 1,3-propylenediamine, N-tridecyl-1,3-propylenediamine, N-myristyl-1,3-propylenediamine, N-pentadecyl-1,3-propylenediamine, N-palmityl-1,3-propylenediamine N-heptadecyl-1,3-propylenediamine, N-oleyl-1,3-propylenediamine, N-stearyl-1,3-propylenediamine, N-isostearyl-1,3-propylenediamine, N-nonadecyl- 1,3-propylenediamine, N-eicosyl-1,3-propylenediamine, N-co Propylenediamines such as nut-1,3-propylenediamine, N-tallow-1,3-propylenediamine, N-hydrogenated tallow-1,3-propylenediamine, N-soybean-1,3-propylenediamine is there.

Further, N-octyl-1,4-butylenediamine, N-nonyl-1,4-butylenediamine, N-decyl-1,4-butylenediamine, N-undecyl-1,4-butylenediamine, N-lauryl- 1,4-butylenediamine, N-tridecyl-1,4-butylenediamine, N-myristyl-1,4-butylenediamine, N-pentadecyl-1,4-butylenediamine, N-palmityl-1,4-butylenediamine N-heptadecyl-1,4-butylenediamine, N-oleyl-1,4-butylenediamine, N-stearyl-1,4-butylenediamine, N-isostearyl-1,4-butylenediamine, N-nonadecyl- 1,4-butylenediamine, N-eicosyl-1,4-butylenediamine, N-coconut-1,4-butylenediamine Emissions, N- tallow-1,4-butylene diamine, N- hydrogenated tallow-1,4-butylene diamine, N- soybean 1,4-butylene diamine, there is butylene diamines and the like.
The above-mentioned organic amine derivatives can be used in combination as appropriate.
As these organic amine derivatives, diamines and amine salts are preferable, and coconut diamine as the diamine, and beef tallow diamine and dioleate as the amine salt are particularly preferable.

The sulfurized fatty acid derivative is a product obtained by sulfurizing animal or vegetable oils or fatty acids, and fatty acids having 8 to 22 carbon atoms are used.
Sulfurized fats and oils as sulfurized fatty acid derivatives refer to sulfides of animal and vegetable oils such as sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil, and sulfurized rice bran oil.
Further, sulfurized fatty acids such as sulfurized oleic acid, sulfurized esters such as methyl sulfide oleate and octyl sulfide oleate, and sulfide mineral oil obtained by dissolving simple sulfur in various mineral oils.
As such sulfurized fatty acid derivatives, those containing 5 to 30% by mass of sulfur are preferable.
Preferred examples include sulfurized fatty acids such as sulfurized oleic acid, sulfurized esters such as methyl sulfide oleate and octyl sulfide oleate, and sulfurized mineral oil obtained by dissolving elemental sulfur in various mineral oils. Of these, sulfurized oleic acid is particularly preferred.

As the surfactant, a nonionic surfactant is preferable, and in particular, a fatty acid ester surfactant can be used.
Examples of the fatty acid ester surfactant include glycerin fatty acid esters as glycerides, sorbitan fatty acid esters as sorbitans, and sucrose fatty acid esters as sucrose. The fatty acid used for these is preferably a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, and these fatty acids can be used alone or in combination.
Examples of the glycerin fatty acid ester include stearic acid monoglyceride, oleic acid monoglyceride, stearic acid, monooleic diglyceride of oleic acid, and the like.
Examples of sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, and the like.
Examples of the sucrose fatty acid ester include sucrose palmitate and sucrose stearate.

Examples of the dibasic acid salt include a salt of an aliphatic dibasic acid having about 4 to 12 carbon atoms, and examples of the aliphatic dibasic acid include adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid.
Examples of the salt include alkali metal salts, alkaline earth metal salts, cobalt salts, manganese salts, lead salts, zinc salts, copper salts, iron salts, zirconium salts, aluminum salts, other rare earth salts, and piperazine salts.
Among these dibasic acid salts, there are preferably alkali metal salts and alkaline earth metal salts . For example, sodium sebacate, sodium suberate, sodium adipate and the like are more preferably used.

Examples of the benzotriazole derivative include benzotriazole.
These can be used together as appropriate.

Further, as the antioxidant, an antioxidant such as amine, phenol, phosphite, sulfur, and dialkyldithiophosphate can be used.
Extreme pressure agents and antiwear agents include sulfurized fats and oils, sulfurized olefins, sulfur compounds such as zinc dithiocarbamate and dithiocarbamate such as molybdenum dithiocarbamate, phosphate esters, acidic phosphate esters, phosphite esters, Phosphorus compounds such as acid phosphites, amine salts of phosphate esters, amine salts of phosphites, amine salts of acid phosphate esters, amine salts of acid phosphites, thiophosphate esters, or dithiophosphorus Sulfur phosphorus compounds such as dithiophosphates such as zinc oxide, molybdenum dithiophosphate, etc. can be used.

In addition, the lubricant composition of the present invention uses other thickeners in combination (mixed use) together with the above-described tricalcium phosphate acting as a thickener. These other thickeners include urea compounds, alkali metal soaps, alkali metal composite soaps, alkaline earth metal soaps, alkaline earth metal composite soaps, alkali metal sulfonates, alkaline earth metal sulfonates, aluminum soaps. , Aluminum composite soap, terephthalate metal salt, clay, silica airgel, polytetrafluoroethylene, and the like, and one or more of these can be used in combination.
Among these, preferred are alkali metal soaps, alkali metal composite soaps, alkali metal sulfonates, alkaline earth metal sulfonates, aluminum soaps, aluminum composite soaps, clays and silica airgels.
Use of these other thickeners in combination is effective in reducing the coefficient of friction under severe lubricating conditions and further improving the wear resistance.

The above-mentioned other thickeners can be mixed with fluorine oil together with tricalcium phosphate to form the present lubricant composition, or a lubricant composition prepared using fluorine oil and tricalcium phosphate. The present lubricant composition can be obtained by mixing a product, a lubricant composition prepared using another thickener and a base oil other than fluorine oil or fluorine oil.
When such other thickeners are used in combination, the rust preventives, anticorrosives, antioxidants, extreme pressure agents, antiwear agents and other additives mentioned above are groups other than the thickeners and fluorine oil. It may be good to add and mix into a lubricant composition made using oil and then mix with a lubricant composition made using fluorine oil and tricalcium phosphate. In this way, an additive which is difficult to mix with the fluorine oil can be easily mixed, which is effective.

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereby.
(Reference Example 1)
As perfluoropolyether U.S. DuPont GPL106: taken 450 g (viscosity 25 mm ² / s at 240mm ² / s, 100 ℃ at 40 ° C.), was kneaded at room temperature tribasic calcium phosphate was added 50 g, three-roll mill And finished in a uniform state to obtain a lubricant composition. The content of tricalcium phosphate is 10% by mass.

(Reference Example 2)
As perfluoropolyether U.S. DuPont GPL107: taken 450 g (viscosity 42mm ² / s at 440mm ² / s, 100 ℃ at 40 ° C.), was kneaded at room temperature tribasic calcium phosphate was added 50 g, three-roll mill And finished uniformly to obtain a lubricant composition. The content of tricalcium phosphate is 10% by mass.

(Reference Example 3)
Take 425 g of FL-100-1000CS (viscosity: 1000 mm ² / s at 25 ° C.) as fluorosilicone, add 75 g of tricalcium phosphate and knead at room temperature, then treat with a three roll mill, A lubricant composition was obtained by finishing uniformly. The content of tricalcium phosphate is 15% by mass.

(Reference Example 4)
A lubricant composition was obtained by mixing 200 g of the lubricant composition of Reference Example 2 and 200 g of the lubricant composition of Reference Example 3 . The content of tricalcium phosphate is 12.5% by mass.

(Examples 1-12, Reference Examples 5-9)
As shown in Tables 3 to 12, the lubricant composition of Reference Example 2 is mixed with a lubricant composition formed of other thickeners of Comparative Examples 4 to 12 described below. .

(Reference Examples 10-18)
Fluorine oil (perfluoropolyether GPL107 manufactured by DuPont, USA) and tricalcium phosphate, succinic acid derivative, beef tallow diamine / dioleic acid salt, coconut diamine, sulfurized oleic acid, stearic acid at each mixing ratio shown in Table 13 to Table 14・ Oleic acid mono-diglyceride, sorbitan tristearate, sodium sebacate, benzotriazole, a mixture of sodium sebacate and benzotriazole, kneaded, treated with a three-roll mill, and finished to a uniform lubricant composition Got.

The succinic acid derivative used above is a succinic acid ester derivative, which is tetrapropenyl succinic acid and 1,3-propanediol half ester shown below. The acid value according to JIS K2501 method is 160 mgKOH / g, and the following formula (13 ), A mixture of compounds represented by formula (14).

The diamine / difatty acid salt used above is shown below.
Diamine / difatty acid salt: N-alkyl (C ₁₄ -C ₁₈ ) trimethylenediamine dioleate (tallow diamine dioleate) represented by the following formula (15).
(Chemical formula 15)
RNH (CH ₂ ) ₃ NH ₂ .2C ₁₇ H ₃₅ COOH (15)
(R = _C 14 ~C ₁₈₎

The coconut diamine used is coconut diamine whose main component is N-dodecyl-1,3-propylenediamine, and has a base number of 440 mgKOH / g according to JIS K2501, and is represented by the following formula (16).
(Chemical formula 16)
R—NH—C ₃ H ₆ —NH ₂ (16)
(R = palm alkyl)

(Comparative Example 1)
Commercially available lithium composite soap grease: “TEXACO STARPLEX 2” from TEXACO
(Comparative Example 2)
Commercially available aluminum composite soap grease: MAGNA INDUSTRIAL Co. Limited "OMEGA57"
(Comparative Example 3)
Commercially available urea grease: “CALTEX RPM SRI OEM2” from CALTEX
(Comparative Example 4)
Commercially available clay-based grease: Shell Aviation Limited “Aero shell grease 22” (ASG-22)
(Comparative Example 5)
Lubricant composition formed from polytetrafluoroethylene: A commercially available lubricant composition (FOMBLIN RT-15) using fluorine oil as the base oil and polytetrafluoroethylene as the thickener.

(Comparative Example 6)
Lubricant composition formed from calcium sulfonate: A commercially available lubricant composition (trade name; Calforex EP grease) using calcium sulfonate as a thickener.
(Comparative Example 7)
Lubricant composition formed from a urea compound: diphenylmethane-4,4′- in 900 g of refined mineral oil (I) having a kinematic viscosity at 100 ° C. of about 33 mm ² / s and a kinematic viscosity at 40 ° C. of about 500 mm ² / s. 0.147 mol (36.88 g) of diisocyanate is reacted with 0.295 mol (38.12 g) of octylamine, then 0.04 mol (0.008 g) of diphenylmethane-4,4′-diisocyanate is mixed with 0.04 mol of laurylamine. A lubricant composition obtained by adding 08 mol (14.92 g) and reacting, and uniformly dispersing with a three-roll mill. The content of the urea compound is 10% by mass.
(Comparative Example 8)
Lubricant composition formed from lithium soap: A lubricant composition obtained by dissolving 600 g of 12-hydroxylithium stearate in 5400 g of the above refined mineral oil (I) and uniformly dispersing it. The content of lithium soap is 10% by mass.
(Comparative Example 9)
Lubricant composition formed with lithium composite soap: After reacting 350 g of 12-hydroxylithium stearate with 50.5 g of lithium hydroxide in 4165 g of the above refined mineral oil (I), 120.65 g of azelaic acid was added to lithium hydroxide 59 Grease obtained by reacting with 0.0 g and uniformly dispersing and treating. The content of the thickener is 10.4% by mass.
(Comparative Example 10)
Lubricant composition formed from calcium soap: Grease obtained by dissolving 300 g of calcium stearate in 2700 g of the above refined mineral oil (I) and uniformly dispersing and treating it. The content of the thickener is 10% by mass.

(Comparative Example 11)
Lubricant composition formed from aluminum composite soap: 158.22 g of benzoic acid and 334.8 g of stearic acid were dissolved in 4272 g of the above-described refined mineral oil (I), and then a commercially available cyclic aluminum oxide propylate lubricant [trade name: Kawa [Algoma manufactured by Ken Fine Chemical Co., Ltd.] 293.64 g was added and reacted, and the resulting soap was uniformly dispersed. The content of the aluminum composite soap is about 11% by mass. The molar ratio of benzoic acid (BA) and stearic acid (FA) was BA / FA = 1.1, and the molar ratio of benzoic acid and aluminum (Al) to stearic acid was (BA + FA) /Al=1.9. .
(Comparative Example 12)
Lubricant composition formed with sodium terephthalamate: In 2700 g of the above refined mineral oil (I), 294.54 g of methyl N-octadecyl terephthalate is reacted with 27.36 g of sodium hydroxide, and uniformly dispersed and treated. Grease obtained by The content of the thickener is 10% by mass.
(Comparative Example 13)
Fluorine oil (II) [perfluoropolyether GPL107 manufactured by DuPont, USA], tricalcium phosphate and calcium sulfonate were kneaded at room temperature at the blending ratio shown in Table 14, and then treated with a three-roll mill to finish uniformly. A lubricant composition obtained.
(Comparative Example 14)
A lubricant composition obtained by kneading fluorine oil (II), tricalcium phosphate and zinc sulfonate at the room temperature shown in Table 14 at room temperature, then treating with a three-roll mill and finishing uniformly.
(Comparative Example 15)
A lubricant composition obtained by kneading fluorine oil (II), tricalcium phosphate and zinc naphthenate at room temperature at the blending ratios shown in Table 14 and then processing with a three-roll mill and finishing uniformly.

(test)
Regarding the lubricant compositions of Examples 1 to 12, Reference Examples 1 to 18, and Comparative Examples 1 to 15, the consistency, heat resistance, high temperature bearing life, load resistance, friction coefficient, wear resistance, bearing rust prevention, etc. Tests were performed as appropriate for evaluation.
(1) Consistency: With respect to the consistency of the grease specified in JIS K2220 (ASTM D1403), the consistency (25 ° C., 60 W) was measured with a 1/4 scale mixer. Moreover, the immiscibility penetration (25 degreeC, 0W) was measured.
(2) Consistency after heating: The sample was packed in a JIS K2220 (ASTM D1403) 1/4 scale blender, the surface was cut flat, and heated at 200 ° C. for 24 hours. Thereafter, the sample was allowed to cool to room temperature while observing changes in the appearance of the sample, and the above-mentioned immiscible penetration (0 W) was measured at a temperature of 25 ° C.
Moreover, the hardness change rate of the sample was calculated | required by following Formula.
Hardness change rate (%) = [(P ₂ −P ₁ ) / P ₂ ] × 100
P ₁ = immiscible penetration P ₂ = pre-test immiscible penetration after the test (3) thin-film evaporation: thickness defined in a wet test method JIS K2246 (1.0 to 2.0 mm) × vertical 60mm × Apply 1.0 ± 0.1g of sample to the central area (50 × 70mm) on one side of a test piece with a width of 80mm, conduct a heating test at 200 ° C for 24 hours, and observe the state of the sample after the test. In addition, the evaporation amount (loss amount) of the sample was determined by mass%.
(4) High temperature bearing life test: A bearing life test was performed in accordance with ASTM D3336 to determine the bearing life time (hours) at 200 ° C.
(5) Load resistance: In accordance with ASTM D2596, a four-ball test was performed under the following conditions, and 50 kgf, 63 kgf, 80 kgf, 100 kgf, 126 kgf, 160 kgf, 200 kgf, 250 kgf up to the fusion load (WL; Weld Load, kgf). , 315 kgf, 400 kgf, 500 kgf, and 600 kgf, the wear scar diameter (mm) of the ball was obtained.
Condition: Number of revolutions; 1770 ± 60 rpm
Time: 10 seconds
Temperature; room temperature

(6) Falex frictional wear test: The friction coefficient 15 minutes after the start of the test and the surface roughness (μm) of the test piece (pin) were determined according to the following conditions (based on IP241 / 65).
Condition: Rotation speed: 290 rpm
Load: 90.7 kg (200 pounds)
Temperature; room temperature,
Time; 15 minutes,
Sample amount: About 1 gram of sample was applied to the test piece. (7) Rust prevention test result: A bearing rust prevention test was conducted under the following conditions based on ASTM D1743-73.
Conditions: Temperature; 52 ° C
Time; 48 hours,
Relative humidity; 100%

(result)
About Examples 1-12 and Reference Examples 1-18 , the result of the test was described in Table 1, Table 3-Table 14 with the composition of the sample.
About Comparative Examples 1-15, the result of the test was described in Table 2, Table 4-Table 12, and Table 14.

(Discussion)
As shown in Table 1, the lubricant compositions of Reference Examples 1 to 4 have a small rate of change in hardness of 5.8% or less even when heated at a high temperature of 200 ° C. for 24 hours, and the evaporation amount of the thin film is also 22% by mass or less. And few.
On the other hand, as shown in Table 2, the commercially available high-temperature greases of Comparative Examples 1 to 3 melted when heated at a high temperature of 200 ° C. for 24 hours, and flowed out of the container, and the change in hardness could not be measured. . Further, the evaporation amount of the thin film is 60% by mass or more, and a solidified state is observed after melting.
Further, those of Reference Examples 1 to 4 has both 200 hours of bearing life at high temperatures bearing life test, four-ball EP test in weld load (WL) is 400kgf in Reference Example 1, Reference Example 2 500 kgf, The reference example 3 is high at 315 kgf and the reference example 4 is high at 600 kgf, and the wear scar diameter (mm) of the ball under each load up to the fusion load is small, and the lubricity is good. It can be seen that those of Reference Examples 1 to 4 are lubricant compositions having excellent heat resistance, wear resistance and load resistance as a whole, and having a long life at high temperatures.
On the other hand, Comparative Examples 1 to 3 have a bearing life of 20 hours and 60 hours in the bearing life test. In the four-ball load resistance (EP) test, the fusion load (WL) is 315 kgf in Comparative Example 1, and Comparative Example 2 It is found that the wear scar diameter (mm) of the ball under each load up to the fusion load (WL) is large and the lubrication performance is insufficient.

Further, Examples 1 to 12 shown in Tables 3 to 12, Reference Examples 5-9 were formed from other thickener of Example 3 or Comparative Examples 4 to Comparative Example 12 in the grease of Example 2 Grease These are mixed at different blending amounts. Reference Example 5 is a mixture of Reference Example 2 and Reference Example 3 at a ratio of 9: 1. Although the wear resistance is slightly low, it is within the allowable limit, and the friction coefficient is better than both. Example 1 is a mixture of Reference Example 2 and Comparative Example 4 at 9: 1, and is superior in friction coefficient and wear resistance to both. Reference Example 6 and Reference Example 7 are obtained by mixing Reference Example 2 and Comparative Example 5 at 9: 1 and 1: 9, which are better in friction coefficient and wear resistance than both. In Example 2 and Example 3 , Reference Example 2 and Comparative Example 6 were mixed at 9: 1 and 1: 9, and the friction coefficient and the abrasion resistance were better than those of both alone, respectively. Example 4 is a mixture of Reference Example 2 and Comparative Example 7 at 9: 1, and is superior in friction coefficient and wear resistance to both. In Example 5 and Example 6 , Reference Example 2 and Comparative Example 8 were mixed at 9: 1 and 5: 5, and the friction coefficient and the wear resistance were better than those of the two alone, respectively. Example 7 is a mixture of Reference Example 2 and Comparative Example 9 at a ratio of 9: 1. The friction coefficient is equal to or better than that of both of them alone, and the wear resistance is excellent. Reference Example 8 and Reference Example 9 are obtained by mixing Reference Example 2 and Comparative Example 10 at 9: 1 and 5: 5, and are better in both friction coefficient and wear resistance than both of them. Example 8, Example 9 and Example 10 were obtained by mixing Reference Example 2 and Comparative Example 11 at 9: 1, 5: 5 and 1: 9, and the friction coefficient was equal or better than both alone, In terms of wear resistance, Example 10 is slightly lower than Reference Example 2 but is within an acceptable range, which is a good result. Example 11 and Example 12 were obtained by mixing Reference Example 2 and Comparative Example 12 at 9: 1 and 5: 5. Example 12 was slightly lower in wear resistance than Reference Example 2, but within an allowable range. In all other cases, better results were obtained than both.

In Tables 13 and 14, a grease composed of fluorine oil and tricalcium phosphate, a succinic acid derivative, beef tallow diamine / dioleic acid, coconut diamine, sulfurized oleic acid, stearic acid / oleic acid mono / diglyceride, sorbitan tristearate, Sodium sebacate, benzotriazole, a combination of sodium sebacate and benzotriazole (Reference Examples 10 to 18) , and calcium sulfonate, zinc sulfonate, zinc naphthenate (Comparative Example 13) Although the result of having examined the effect of ~ 15) is shown, the thing of Reference Examples 10-18 shows that generation | occurrence | production of rust is not seen but a rust prevention effect is high. On the other hand, in general calcium sulfonate, zinc sulfonate, and zinc naphthenate, which are generally known rust preventive agents, rust is generated as shown in Comparative Examples 13 to 15, and the rust preventive effect cannot be obtained. I understand that.

Claims (5)

Fluorine oil containing at least one of perfluoropolyether or fluorosilicone , 1 to 40% by mass of tribasic calcium phosphate as a thickener, and a urea compound having further thickening action, alkali metal A lubricant composition comprising at least one of soap, alkali metal composite soap, alkali metal sulfonate, alkaline earth metal sulfonate, aluminum soap, aluminum composite soap, terephthalate metal salt, clay, and silica airgel . The above-mentioned further thickening action is at least one of alkali metal soap, alkali metal composite soap, alkali metal sulfonate, alkaline earth metal sulfonate, aluminum soap, aluminum composite soap, clay and silica airgel. The lubricant composition as described . Alkali metal salts of dibasic acids, alkaline earth metal salts of dibasic acids, benzotriazole derivatives, benzothiazole derivatives, benzimidazole derivatives, according to claim at least one selected from the thiocarbamate is further included one or 2. The lubricant composition according to 2. The lubricant composition according to claim 3 , wherein the alkali metal salt of the dibasic acid is sodium sebacate. The lubricant composition according to claim 3 , wherein the benzotriazole derivative is benzotriazole.