JP2020147549A - Zinc dithiophosphate manufacturing method, and method of improving odor of zinc dithiophosphate - Google Patents

Abstract

To provide a zinc dithiophosphate manufacturing method for obtaining zinc dithiophosphate improved in odor.SOLUTION: A zinc dithiophosphate manufacturing method comprises mixing, under a certain condition, an amine compound represented by the general formula (1) in the figure with zinc dithiophosphate having odor synthesized using zinc oxide, an alcohol compound having a C4-14 hydrocarbon group and phosphorus pentasulfide. (In the formula, R1 represents a C4-14 hydrocarbon group, and R2 represents a hydrogen atom or a C4-14 hydrocarbon group.)SELECTED DRAWING: None

Description

The present invention relates to a method for producing zinc dithiophosphate having an improved odor and a method for improving the odor of zinc dithiophosphate.

In the fields of lubricating oil, processing oil, grease, fuel oil and the like, zinc dithiophosphate is used as an additive for improving the lubricity and extreme pressure of various fluids. Since zinc dithiophosphate can exhibit excellent extreme pressure by adjusting its alkyl group structure and the like, zinc dithiophosphate having various structures has been developed (for example, Patent Documents 1 to 3).

However, while zinc dithiophosphate exhibits high antioxidant performance and extreme pressure as an additive, it has a practical problem that zinc dithiophosphate having an odor can be obtained by a usual synthetic method. As a countermeasure against such a problem, as in the method described in Patent Document 4, the structure and characteristics of each raw material are strictly selected to control the reaction, and the material mixing and the reaction are carried out in an ice-cooled environment. A method for improvement has been proposed by the above method. However, when such a method is used, there are practical problems such as an increase in procurement cost of raw materials to be used and an increase in the scale of equipment for treating hydrogen sulfide generated in the reaction process.

Special Publication No. 48-37251 JP-A-47-32005 Japanese Unexamined Patent Publication No. 3-223295 Japanese Unexamined Patent Publication No. 11-322771

Accordingly, an object of the present invention to provide a method for improving the odor of zinc dithiophosphate in simple manufacturing process Contact and convenient means of zinc dithiophosphate odor was improved.

As a result of diligent studies to solve the above problems, the present inventors have found that zinc dithiophosphate having an improved odor can be obtained by a method for producing zinc dithiophosphate including a specific step, and completed the present invention. It was.

That is, the present invention comprises a first step of reacting diphosphorus pentasulfide with an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms.
In the second step of adding zinc oxide to the product obtained in the first step to neutralize it,
A dithiophosphate comprising a third step of adding an amine compound represented by the following general formula (1) to the product obtained in the second step and mixing at 20 to 130 ° C. for 10 minutes to 10 hours. This is a method for producing zinc acid.

(In the formula, R ¹ represents a hydrocarbon group having 4 to 14 carbon atoms, and R ² represents a hydrogen atom or a hydrocarbon group having 4 to 14 carbon atoms).

The present invention also provides a method for improving the odor of zinc dithiophosphate, in which an amine compound represented by the above general formula (1) is added to zinc dithiophosphate and mixed at 20 to 130 ° C. for 10 minutes to 10 hours. To do.

According to the present invention, it is possible to provide a method for producing zinc dithiophosphate having an improved odor by using a simple means of mixing a specific amine compound. Further, the present invention can reduce the odor of zinc dithiophosphate by a simple means of mixing a specific amine compound.

In the present invention, as a first step, diphosphorus pentasulfide is reacted with an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms. The product obtained by this first step is dithiophosphate. The method for reacting diphosphorus pentasulfide with an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms is not particularly limited, and for example, JP-A-48-37551, JP-A-47-32005, JP-A-11. In the method for synthesizing dithiophosphate described in No. -322771 and the like, a method using diphosphorus pentasulfide and an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms as raw materials can be mentioned. The diphosphorus pentasulfide used in the present invention is not particularly limited, and known ones can be used.

Examples of the alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms used in the step of synthesizing dithiophosphate as the first step include an alcohol compound having an alkyl group having 4 to 14 carbon atoms and an alcohol compound having 6 to 14 carbon atoms. Examples thereof include alcohol compounds having an aryl group, and from the viewpoint of extreme pressure and odor of the obtained zinc dithiophosphate, it is preferable to use at least one alcohol compound having an alkyl group having 4 to 14 carbon atoms as the alcohol compound. .. Examples of such alcohol compounds having an alkyl group having 4 to 14 carbon atoms include butanol, isobutanol, pentanol, isopentanol, hexanol, heptanol, isoheptanol, octanol, isooctanol, nonanol, isononanol, and decanol. , Isodecanol, undecanol, isoundecanol, dodecanol, isododecanol, tridecanol, isotridecanol, tetradecanol, isotetradecanol and the like, among which have an alkyl group having 4 to 12 carbon atoms. It is more preferable to use at least an alcohol compound, it is even more preferable to use only an alcohol compound having an alkyl group having 4 to 12 carbon atoms, and it is particularly preferable to use only an alcohol compound having an alkyl group having 8 or 12 carbon atoms. .. In the present invention, even if one type of alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms is used as the alcohol compound, two or more kinds of alcohol compounds having a hydrocarbon group having 4 to 14 carbon atoms are used. May be good.

The amount of diphosphous pentasulfide used for the synthesis of dithiophosphate and the alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms is not particularly limited, but the yield of zinc dithiophosphate and the characteristics of the obtained zinc dithiophosphate are considered from the viewpoint. Therefore, for example, it is preferable to use 3.8 to 4.8 mol, preferably 4.0 to 4.4 mol of the alcohol compound with respect to 1 mol of diphosphophosphate pentasulfide.

The conditions for reacting diphosphous pentasulfide with an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms are not particularly limited, but for example, while blowing nitrogen gas, the temperature is 40 to 200 ° C., more preferably 60. A method of obtaining dithiophosphate while producing hydrogen sulfide as a by-product can be used by reacting at ~ 160 ° C. for 1 to 12 hours. In the step of synthesizing dithiophosphate, dithiophosphate that can be preferably used in the present invention can be synthesized by using the above-mentioned method.

The present invention includes, as a second step, a step of synthesizing zinc dithiophosphate by adding zinc oxide to the product obtained in the first step, that is, zinc oxide and neutralizing it. The zinc dithiophosphate obtained in this step has an odor and is different from the final object of the present invention, zinc dithiophosphate having an improved odor.

The step of synthesizing zinc dithiophosphate, which is the second step of the method for producing zinc dithiophosphate of the present invention, is a step of adding zinc oxide to the dithiophosphate obtained by the above-mentioned step of synthesizing dithiophosphate to neutralize it. is there. The conditions for adding zinc oxide to dithiophosphate to neutralize it are not particularly limited, and for example, the conditions described in JP-A-48-37551, JP-A-47-32005, JP-A-11-322771, etc. Specifically, for example, 1.0 to 2.0 mol, more preferably 1.1 to 1.9 mol, still more preferably the dithiophosphate obtained with respect to 1 mol of zinc oxide. Zinc dithiophosphate is prepared by using 1.2 to 1.8 mol of zinc dithiophosphate under normal pressure at 20 to 120 ° C., more preferably 40 to 100 ° C., even more preferably 60 to 80 ° C. for 3 to 12 hours. Can be synthesized. When neutralizing dithiophosphate with zinc oxide, zinc compounds such as zinc hydroxide and zinc carbonate may be used in combination with zinc oxide, and reactions such as water and zinc nitrate may be used to control the reactivity. Accelerators and the like may be added. Further, after the reaction, water produced as a by-product may be distilled off under reduced pressure, or unreacted solid matter such as zinc oxide may be removed by filtration.

In the present invention, as a third step, an amine compound represented by the general formula (1) is added to zinc dithiophosphate having an odor, which is a product obtained in the second step, and the temperature is 20 to 130 ° C. Including the step of mixing for 10 minutes to 10 hours.

R ¹ of the general formula (1) represents a hydrocarbon group having 4 to 14 carbon atoms. Examples of such a group include a linear alkyl group having 4 to 14 carbon atoms, a branched alkyl group having 4 to 14 carbon atoms, a linear alkenyl group having 4 to 14 carbon atoms, and a branched alkenyl group having 4 to 14 carbon atoms. , Alicyclic hydrocarbon groups having 4 to 14 carbon atoms, aromatic hydrocarbon groups having 6 to 14 carbon atoms, and the like. Among these, from the viewpoint of improving odor and maintaining various properties, R ¹ is preferably a linear alkyl group having 4 to 14 carbon atoms or a branched alkyl group having 4 to 14 carbon atoms, and specifically, butyl. Group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, It is preferably a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, or an isotetradecyl group. Further, it is more preferably a linear alkyl group having 6 to 14 carbon atoms or a branched alkyl group having 6 to 14 carbon atoms, and a linear alkyl group having 8 to 13 carbon atoms or a branched alkyl group having 8 to 13 carbon atoms. Is even more preferable. In the present invention, one kind or two or more kinds of amine compounds represented by the general formula (1) can be used.

R ² of the general formula (1) represents a hydrogen atom or a hydrocarbon group having 4 to 14 carbon atoms. Examples of such hydrocarbon groups include a linear alkyl group having 4 to 14 carbon atoms, a branched alkyl group having 4 to 14 carbon atoms, a linear alkenyl group having 4 to 14 carbon atoms, and a branched hydrocarbon group having 4 to 14 carbon atoms. Examples thereof include alkenyl groups, alicyclic hydrocarbon groups having 4 to 14 carbon atoms, and aromatic hydrocarbon groups having 6 to 14 carbon atoms. R ² is preferably a linear alkyl group having 4 to 14 carbon atoms or a branched alkyl group having 4 to 14 carbon atoms from the viewpoint of improving odor and maintaining various properties. Specifically, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, Examples thereof include an undecyl group, an isoundecyl group, a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group and an isotetradecyl group.

Amine compounds represented by the general formula (1), from the viewpoint of maintaining the odor-modifying and properties, R ¹ is a linear alkyl group or branched alkyl group having a carbon number of 4 to 14 4 to 14 carbon atoms, It is particularly preferred that R ² is the same group as R ¹ . Examples of such amine compounds include di-butylamine, di-pentylamine, di-hexylamine, di-heptylamine, di-octylamine, di-ethylhexylamine, di-nonylamine, di-decylamine, and diun. Examples thereof include decylamine, didodecylamine, di-tridecylamine, di-tetradecylamine, etc. Among these, di-octylamine, di-ethylhexylamine, di-nonylamine, di-decylamine, di-undecylamine and the like. Amines, diedodesylamines and ditolideylamines are preferred. Further, in the present invention, one kind of amine compound represented by the general formula (1) may be used, or two or more kinds of amine compounds represented by the general formula (1) may be used. The amine compound used in the third step of the present invention may be a commercially available product or may be produced by a known production method.

As the amine compound represented by the general formula (1) used in the third step of the present invention, the average of the alkyl groups of R ¹ and R ² is averaged from the viewpoint of improving the odor of the obtained zinc dithiophosphate and maintaining various properties. The number of carbon atoms (representing the number of carbon atoms of R ¹ when R ² is a hydrogen atom) is preferably 6 to 13, more preferably 7 to 13, and even more preferably 8 to 13. This average carbon number (hereinafter, may be referred to as "average carbon number of the alkyl group of the amine compound") is the carbon number of the alkyl group of R ¹ and R ² when the amine compound used is one kind. It can be calculated by averaging, and when two or more kinds of amine compounds are used, it can be calculated based on the average carbon number of the alkyl group of each amine compound and the molar ratio of each amine compound.

In the third step of the present invention, the amount of the amine compound added to zinc dithiophosphate, which is the product of the second step, is not particularly limited, but the odor of zinc dithiophosphate, which is the final target product, is improved and various properties are maintained. From this point of view, the amount of the amine compound added is preferably 0.01 to 1.0 parts by mass, preferably 0.1 to 0.8 parts by mass, based on 100 parts by mass of zinc dithiophosphate, which is the product of the second step. It is more preferably parts by mass, and even more preferably 0.2 to 0.6 parts by mass.

The third step of the present invention is a step of adding an amine compound to zinc dithiophosphate, which is a product obtained in the second step, and mixing at 20 to 130 ° C. for 10 minutes to 10 hours. In the present invention, by mixing under such conditions, the odor can be improved while maintaining various properties such as extreme pressure property and antioxidant property of zinc dithiophosphate, which is the final target product. At this time, from the viewpoint of further improving the odor of zinc dithiophosphate, which is the final target product, the temperature is preferably 60 to 120 ° C., more preferably 90 to 110 ° C., preferably 1 hour to under reduced pressure to pressurized environment. It may be mixed for 7 hours, more preferably 2 to 5 hours. Further, it is preferable that this step is performed under normal pressure.

In the method for producing zinc dithiophosphate of the present invention, an alcohol having at least one alkyl group having 4 to 14 carbon atoms as an alcohol compound is used from the viewpoint of improving the odor of the finally obtained zinc dithiophosphate and maintaining various properties. It is preferable to use a compound, and at this time, the difference between the average carbon number of the alkyl group of the alcohol compound having an alkyl group having 4 to 14 carbon atoms and the average carbon number of the amine compound used in the third step is 8 or less. Is preferable. In the present invention, with such a configuration, various properties of zinc dithiophosphate can be maintained at a higher level. In the present invention, when two or more kinds of alcohol compounds are used, the average carbon number calculated based on the carbon number and molar ratio of the alkyl group of each alcohol compound used is treated as the average carbon number of the alcohol compound. In the present invention, from the viewpoint of maintaining various properties of zinc dithiophosphate, the average carbon number of the alkyl group of the alcohol compound used in the production process of dithiophosphate and the average carbon number of the amine compound used in the third step The difference is more preferably 0 or more and 6 or less, and even more preferably 0 or more and 4 or less.

The method for improving the odor of zinc dithiophosphate of the present invention is a method in which an amine compound represented by the following general formula (1) is added to zinc dithiophosphate and mixed at 20 to 130 ° C. for 10 minutes to 10 hours.

(In the formula, R ¹ represents a hydrocarbon group having 4 to 14 carbon atoms, and R ² represents a hydrogen atom or a hydrocarbon group having 4 to 14 carbon atoms).

The zinc dithiophosphate used in the method for improving the odor of zinc dithiophosphate of the present invention is not particularly limited as long as it has a structure in which two thiophosphate groups or an alkyl derivative thereof are coordinated with a zinc element, and is, for example, the following general formula (2). ) Is represented by zinc dithiophosphate.

R ^{3 to} R ⁶ of the general formula (2) independently represent hydrocarbon groups having 4 to 14 carbon atoms. Examples of such a group include a linear alkyl group having 4 to 14 carbon atoms, a branched alkyl group having 4 to 14 carbon atoms, a linear alkenyl group having 4 to 14 carbon atoms, and a branched alkenyl group having 4 to 14 carbon atoms. , Alicyclic hydrocarbon groups having 4 to 14 carbon atoms, aromatic hydrocarbon groups having 6 to 14 carbon atoms, and the like. In the present invention, one kind or two or more kinds of zinc dithiophosphate represented by the general formula (1) can be used. Among these, from the viewpoint of various properties of zinc dithiophosphate, it is preferable that R ^{3 to} R ⁶ are independently linear alkyl groups having 4 to 14 carbon atoms or branched alkyl groups having 4 to 14 carbon atoms, respectively. Specifically, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an ethylhexyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, It is preferably an undecyl group, an isoundecyl group, a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, or an isotetradecyl group.

R ^{3 to} R ⁶ of the general formula (2) may be the same hydrocarbon group or different hydrocarbon groups, respectively, but from the viewpoint of odor improvement and various characteristics, R ³ and R ⁶ and R may be used. It is preferable that ⁴ and R ⁵ are the same hydrocarbon group, respectively, and it is particularly preferable that R ^{3 to} R ⁶ are all the same group. Such zinc dithiophosphate may be a commercially available product, or may be synthesized by a known method, for example, the above-mentioned method for synthesizing zinc dithiophosphate (the first and second steps).

Examples of the amine compound represented by the general formula (1) used in the method for improving the odor of zinc dithiophosphate of the present invention include amine compounds having the above-mentioned structure. In the method for improving the odor of zinc dithiophosphate of the present invention, from the viewpoint of improving the odor and maintaining various properties, in the general formula (1), R ¹ is a linear alkyl group having 4 to 14 carbon atoms or a linear alkyl group having 4 to 14 carbon atoms. It is particularly preferable that it is a branched alkyl group and R ² is the same group as R ¹ . From the viewpoint of maintaining the odor-modifying and properties of the resulting zinc dithiophosphate, an average carbon number of the alkyl group of R ¹ and R ² (if R ² is a hydrogen atom represents the number of carbon atoms in R ¹⁾ is It is preferably 6 to 13, more preferably 7 to 13, and even more preferably 8 to 13.

In the method for improving the odor of zinc dithiophosphate of the present invention, from the viewpoint of maintaining various properties of zinc dithiophosphate at a higher level, the average carbon number of the four alkyl groups of zinc dithiophosphate (for example, the formula (2)) The difference between the average carbon number of R ^{3 to} R ⁶ ) and the average carbon number of the amine compound represented by the general formula (1) is preferably 8 or less, more preferably 0 or more and 6 or less. It is even more preferable that it is 0 or more and 4 or less.

The method for adding the amine compound to zinc dithiophosphate in the method for improving the odor of zinc dithiophosphate of the present invention is not particularly limited, and for example, 0.01 to 1.0 part by mass of amine with respect to 100 parts by mass of zinc dithiophosphate. Examples thereof include a method of adding the compound in a reduced pressure to pressurized environment including 20 to 130 ° C. and normal pressure. At this time, from the viewpoint of improving the odor of the obtained zinc dithiophosphate and maintaining various properties, the amount of the amine compound added is preferably 0.1 to 0.8 parts by mass with respect to 100 parts by mass of zinc dithiophosphate. , 0.2 to 0.6 parts by mass is even more preferable.

In the method for improving the odor of zinc dithiophosphate of the present invention, after adding an amine compound to zinc dithiophosphate by the above-mentioned method or the like, the mixture is mixed at 20 to 130 ° C. under normal pressure for 10 minutes to 10 hours under reduced pressure to pressurized environment. How to do it. In the present invention, by using such a method, the odor can be improved while maintaining various properties such as extreme pressure property and antioxidant property of zinc dithiophosphate. From the viewpoint of further improving the odor of the obtained zinc dithiophosphate, it is preferable to mix at 60 to 120 ° C., and it is preferable to mix at 90 to 110 ° C. Further, from the viewpoint of improving the odor of the obtained zinc dithiophosphate and maintaining various properties, it is preferable to mix for 1 hour to 7 hours, and more preferably for 2 hours to 5 hours. Further, it is preferable to mix the amine compound under normal pressure.

The zinc dithiophosphate obtained by using the method for producing zinc dithiophosphate of the present invention and the method for improving the odor of zinc dithiophosphate can be used for various purposes as an antioxidant, an antioxidant, an anti-wear agent, etc., respectively. , For example, engine oil, gear oil, turbine oil, hydraulic oil, flame-retardant hydraulic fluid, refrigerating machine oil, compressor oil, vacuum pump oil, bearing oil, metal processing oil, plastic processing oil, insulating oil, sliding surface oil, It can be used in lubricating oil compositions such as rock drill oil, metal processing oil, plastic processing oil, heat treatment oil, and grease, and various fuel oil compositions. Among these, it is preferably used for engine oil, metalworking oil, plastic processing oil, bearing oil, and grease, and most preferably for engine oil, metalworking oil, and plastic processing oil.

The base oil that can be used in the lubricating oil composition containing zinc dithiophosphate obtained by the present invention is not particularly limited, and mineral base oils, chemically synthesized base oils, animal and plant base oils, and these are appropriately used according to the purpose of use and conditions. It can be selected from mixed base oil and the like.

As the mineral base oil, for example, a distillate obtained by atmospherically distilling a paraffin-based crude oil, a naphthenic-based crude oil or an intermediate basic crude oil, or distilling a residual oil of atmospheric distillation under reduced pressure, or these are usually used. Examples thereof include refined oils obtained by refining according to the method, specific examples thereof include solvent refined oils, hydrogenated refined oils, dewazing treated oils and white clay treated oils.

Examples of the chemically synthesized base oil include poly-α-olefin, polyisobutylene (polybutene), monoester, diester, polyol ester, silicic acid ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, alkylbenzene and GTL. Examples include base oil. Among these, poly-α-olefins, polyisobutylene (polybutene), diesters, polyol esters and the like can be used for general purposes. Examples of the poly-α-olefin include those obtained by polymerizing or oligomerizing 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene and the like, or hydrogenating these. And so on. Examples of the diester include dibasic acids such as glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanolic acid, and diesters of alcohols such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol. Examples of the polyol ester include polyols such as neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and caproic acid, caprylic acid, lauric acid, capric acid, myristic acid and palmitin. Examples thereof include esters with fatty acids such as acid, stearic acid and oleic acid.

Animal and plant base oils include, for example, castor oil, olive oil, cacao butter, sesame oil, rice bran oil, saflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, sunflower oil, cottonseed oil and palm. Examples thereof include vegetable fats and oils such as oil, beef fat, pork fat, milk fat, fish oil and animal fats and oils such as whale oil.
Any one of the above base oils may be used, or two or more of them may be used. If necessary, a highly refined base oil obtained by highly refining these base oils to reduce the amount of impurities such as sulfur may be used.

The content of zinc dithiophosphate described above in the lubricating oil composition containing zinc dithiophosphate obtained by the production method of the present invention or treated by the odor improving method of the present invention is not particularly limited, but from the viewpoint of extreme pressure and the like. Therefore, for example, the lubricating oil composition preferably contains zinc dithiophosphate in an amount of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of zinc dithiophosphate.

The lubricating oil composition containing zinc dithiophosphate obtained by the present invention has viewpoints of friction characteristics, abrasion characteristics, oxidation stability, temperature stability, storage stability, cleanliness, rust prevention, corrosion prevention, handleability and the like. Therefore, a known additive may be further contained depending on the purpose of use. For example, friction reducing agents, abrasion resistance agents, antioxidants, oiliness improving agents, cleaning agents, dispersants, viscosity index improving agents, pour point lowering agents, rust preventives, corrosion inhibitors, metal inactivating agents, defoaming agents. One kind or two or more kinds of agents may be contained, and these additives may be contained in a total amount of, for example, 0.01 to 50% by mass with respect to the total amount of the lubricating oil composition.

Examples of the friction reducing agent include organic molybdenum compounds such as molybdenum dithiocarbamate and molybdenum dithiophosphate. Examples of the molybdenum dithiocarbamate include molybdenum dithiocarbamate having a hydrocarbon group having 1 to 20 carbon atoms, and among these, molybdenum dithiocarbamate having a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms is preferable. The preferable blending amount of molybdenum dithiocarbamate is an amount such that the molybdenum content in the lubricating oil composition is 50 to 3000 mass ppm, more preferably 100 to 2000 mass ppm, and further preferably 200 to 1500 mass ppm. It is an amount that becomes ppm.

Abrasion resistant agents include, for example, sulfide fats and oils, olefin polysulfide, sulfide olefin, dibenzyl sulfide, ethyl-3-[[bis (1-methylethoxy) phosphinochi oil] thio] propionate, tris-[(2, or 4) -Isoalkylphenol] thiophosphate, 3- (di-isobutoxy-thiophosphorylsulfanyl) -2-methyl-propionic acid, triphenylphosphorothionate, β-dithiophosphorylated propionic acid, methylenebis (dibutyldithiocarbamate) ), O, O-diisopropyl-dithiophosphoryl ethyl propionate, 2,5-bis (n-nonyldithio) -1,3,4-thiadiazol, 2,5-bis (1,1,3,3-) Sulfur-based abrasion resistant agents such as tetramethylbutanthio) 1,3,4-thiazylazole and 2,5-bis (1,1,3,3-tetramethyldithio) -1,3,4-thiazylazole; monooctyl Phenyl phosphate, dioctyl phosphate, trioctyl phosphate, monobutyl phosphate, dibutyl phosphate, tributyl phosphate, monophenyl phosphate, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, monoisopropylphenyl phosphate , Diisopropylphenyl phosphate, triisopropylphenyl phosphate, monotersial butyl phenyl phosphate, di-tert-butyl phenyl phosphate, tri-tert-butyl phenyl phosphate, triphenyl thiophosphate, monooctyl phosphite, dioctyl phos. Fight, Trioctylphosphite, Monobutylphosphite, Dibutylphosphite, Tributylphosphite, Monophenylphosphite, Diphenylphosphite, Triphenylphosphite, Monoisopropylphenylphosphite, Diisopropylphenylphosphite, Triisopropylphenylphosphite , Mono-tert-butylphenylphosphite, di-tert-butylphenylphosphite, and tri-tert-butylphenylphosphite and other phosphorus-based compounds; naphthenic acid metal salt, fatty acid metal salt, phosphoric acid metal salt, phosphoric acid. Organic metal compounds such as ester metal salts and phosphite ester metal salts (excluding zinc dithiophosphate obtained by the present invention); Other examples include boron compounds, alkylamine salts of mono and dihexyl phosphate, phosphate ester amine salts, and mixtures of triphenylthiophosphate and tert-butylphenyl derivatives. The preferable blending amount of the wear resistant agent is 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, based on the total amount of the lubricating oil composition.

Examples of the antioxidant include 2,6-di-tershaributylphenol (hereinafter, tertiary-butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol, 2,6. -Di-t-Butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylenebis (2,6-methylenebis) Di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4'-bis (2-methyl-6-t-butylphenol), 2,2'-methylenebis (2,2'-methylenebis) 4-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4 '-Isopropyridenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol, 3- t-Butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3) , 5-Di-t-Butylphenyl) stearyl propionate, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate oleyl, 3- (4-hydroxy-3,5-di-t) Dodecyl-butylphenyl) propionate, decyl 3- (4-hydroxy-3,5-di-t-butylphenyl) decylpropionate, tetrakis {3- (4-hydroxy-3,5-di-t-butylphenyl) Propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid And glycerin monooleyl ether, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid butylene glycol diester, 3- (4-hydroxy-3,5-di-t-butylphenyl) ) Propionic acid thiodiglycoldiester, 4,4'-thiobis (3-methyl-6-) t-Butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl -Α-Dimethylamino-p-cresol, 2,6-di-t-butyl-4- (N, N'-dimethylaminomethylphenol), bis (3,5-di-t-butyl-4-hydroxybenzyl) ) Sulfide, Tris {(3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, Tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1, 3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl} sulfide , 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4-t-butyl-3-hydroxy) Benzyl sulfide), 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine, 2,2-thio- {diethyl-bis- 3- (3,5-di-t-butyl-4-hydroxyphenyl)} propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinamide), 3,5 -Di-t-butyl-4-hydroxy-benzyl-phosphate diester, bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfate, 3,9-bis [1,1-dimethyl-2- {Β- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene , Bis {3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyl acid} glycol ester and other phenolic antioxidants; 1-naphthylamine, phenyl-1-naphthylamine, p- Octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl- Naftylamine-based antioxidants such as 1-naphthylamine and phenyl-2-naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p- Phenylene diamine, N, N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1 , 3-Dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine and other phenylenediamine-based antioxidants; dipyridylamine, Diphenylamine, p, p'-di-n-butyldiphenylamine, p, p'-di-t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p' -Dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyldiphenylamine, p, p'-dystyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α) , Α-Dimethylbenzoyl) Diphenylamine-based antioxidants such as diphenylamine, p-isopropoxydiphenylamine, dipyridylamine; phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazine carboxylic acid ester, phenoserena Examples thereof include phenothiazine-based antioxidants such as gin. The preferable blending amount of these antioxidants is 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, based on the total amount of the lubricating oil composition.

Examples of the oiliness improver include higher alcohols such as oleyl alcohol and stearyl alcohol; fatty acids such as oleic acid and stearyl acid; esters such as oleyl glycerin ester, stearyl glycerin ester and lauryl glycerin ester; lauryl amide and oleyl amide. , Stearylamides and the like; amines such as laurylamine, oleylamine and stearylamine (excluding amine compounds represented by the general formula (1)). The preferable blending amount of these oiliness improvers is 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, based on the total amount of the lubricating oil composition.

Examples of the cleaning agent include sulfonates such as calcium, magnesium and barium, phenates, salicylates, phosphates and hyperbasic salts thereof. Among these, a hyperbasic salt is preferable, and among the superbasic salts, those having a TBN (total base value) of 30 to 500 mgKOH / g are more preferable. Further, a salicylate-based cleaning agent free of phosphorus and sulfur atoms is preferable. The preferable blending amount of these cleaning agents is 0.5 to 10% by mass, more preferably 1 to 8% by mass, based on the total amount of the lubricating oil composition.

The ashless dispersant can be used without particular limitation as long as it is an ashless dispersant used as a lubricant. For example, a linear or branched alkyl group having 40 to 400 carbon atoms or an alkenyl group is used as a molecule. Examples thereof include a nitrogen-containing compound having at least one of them, or a derivative thereof. Specific examples thereof include succinic acid imide, succinic acid amide, succinic acid ester, succinic acid ester-amide, benzylamine, polyamine, polysuccinic acid imide, and Mannich base, and derivatives thereof include hoe in these nitrogen-containing compounds. Examples thereof include boron compounds such as acids and borates, phosphorus compounds such as thiophosphate and thiophosphate, organic acids and hydroxypolyoxyalkylene carbonates. If the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility of the compound in the base oil may decrease, while if the alkyl group or alkenyl group has more than 400 carbon atoms, the lubricating oil composition Low temperature fluidity may deteriorate. The preferable blending amount of these ashless dispersants is 0.5 to 10% by mass, more preferably 1 to 8% by mass, based on the total amount of the lubricating oil composition.

Examples of the viscosity index improver include poly (C1-18) alkyl (meth) acrylate, (C1-18) alkyl acrylate / (C1-18) alkyl (meth) acrylate copolymer, diethylaminoethyl (meth) acrylate /. (C1-18) Alkyl (meth) acrylate copolymer, ethylene / (C1-18) alkyl (meth) acrylate copolymer, polyisobutylene, polyalkylstyrene, ethylene / propylene copolymer, styrene / maleic acid ester Examples include polymers, styrene / isoprene hydride copolymers and the like. Alternatively, a dispersion-type or multifunctional viscosity index improver imparted with dispersion performance may be used. The weight average molecular weight is about 10,000 to 1,500,000. The preferable blending amount of these viscosity index improvers is 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total amount of the lubricating oil composition.

Examples of the pour point lowering agent include polyalkyl methacrylate, polyalkyl acrylate, polyalkyl styrene, polyvinyl acetate and the like, and the weight average molecular weight is 1000 to 100,000. The preferable blending amount of these pour point lowering agents is 0.005 to 3% by mass, more preferably 0.01 to 2% by mass, based on the total amount of the lubricating oil composition.

Examples of the rust preventive agent include sodium nitrite, paraffin wax calcium oxide, paraffin wax magnesium oxide, beef fatty acid alkali metal salt, alkaline earth metal salt or amine salt, alkenyl succinic acid or alkenyl succinic acid half ester (alkenyl). The molecular weight of the group is about 100 to 300), sorbitan monoester, nonylphenol ethoxylate, lanolin fatty acid calcium salt and the like. The preferable blending amount of these rust preventives is 0.01 to 3% by mass, more preferably 0.02 to 2% by mass, based on the total amount of the lubricating oil composition.

Examples of the corrosion inhibitor and metal inactivating agent include triazole, triltriazole, benzotriazole, benzoimidazole, benzothiazole, benzothiazazole or derivatives of these compounds, 2-hydroxy-N- (1H-1,2). , 4-Triazole-3-yl) benzamide, N, N-bis (2-ethylhexyl)-[(1,2,4-triazole-1-yl) methyl] amine, N, N-bis (2-ethylhexyl) -[(1,2,4-Triazole-1-yl) methyl] amine and 2,2'-[[(4 or 5 or 1)-(2-ethylhexyl) -methyl-1H-benzotriazole-1-methyl ] Imino] Bisethanol, etc., and others include bis (poly-2-carboxyethyl) phosphinic acid, hydroxyphosphonoacetic acid, tetraalkylthiuram disulfide, N'1, N'12-bis (2-hydroxybenzoyl). ) Dodecandihydrazide, 3- (3,5-di-t-butyl-hydroxyphenyl) -N'-(3- (3,5-di-tert-butyl-hydroxyphenyl) propanoyl) Propanehydrazide, tetrapro Estases of penylsuccinic acid and 1,2-propanediol, disodium sebacate, (4-nonylphenoxy) acetic acid, alkylamine salts of mono and dihexyl phosphate, sodium salts of tolyltriazole and (Z) -N-methyl Examples thereof include N- (1-oxo9-octadecenyl) glycine. The preferable blending amount of the corrosion inhibitor and the metal inactivating agent is 0.01 to 3% by mass, more preferably 0.02 to 2% by mass, based on the total amount of the lubricating oil composition.

Examples of the defoaming agent include polydimethylsilicone, dimethylsilicone oil, trifluoropropylmethylsilicone, colloidal silica, polyalkylacrylate, polyalkylmethacrylate, alcohol ethoxy / propoxylate, fatty acid ethoxy / propoxylate and sorbitan partial fatty acid ester. Can be mentioned. The preferable blending amount of these defoaming agents is 0.001 to 0.1% by mass, more preferably 0.001 to 0.01% by mass, based on the total amount of the lubricating oil composition.

Hereinafter, the details of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following examples and the like,% is based on mass unless otherwise specified.

<Synthesis of zinc dithiophosphate 1>
A flask equipped with a stirring rod, a stirring seal, a thermometer, a reflux condenser and a nitrogen introduction tube, and connected to a caustic soda water trap bottle for hydrogen sulfide absorption was filled with 745 g (4.0 mol) of n-dodecal, followed by disulfide disulfide. 222 g (1.0 mol) of phosphorus was charged while paying attention to foaming and heat generation accompanying the generation of hydrogen sulfide, heated to 100 to 110 ° C., refluxed for 5 hours while blowing nitrogen, and then cooled. A calculated amount of hydrogen sulfide was generated to obtain 932 g (2.0 mol) of didodecyldithiophosphate (first step). To 466 g (1.0 mol) of the obtained didodecyl dithiophosphate, 24 g (0.3 mol) of zinc oxide was charged and reacted at 60 to 80 ° C. for 2 hours at normal pressure, and then 100 to 110 ° C., 10 Torr or less. Zinc dithiophosphate 1, which is a linear alkyl group having 12 carbon atoms in each of R ^{3 to} R ⁶ in the general formula (2), was synthesized by dehydration for 1 hour (second step).

<Synthesis of zinc dithiophosphate 2>
Zinc dithiophosphate except that n-butanol (2.0 mol) and 2-ethylhexanol (2.0 mol) were used instead of n-dodecanol (the average number of carbon atoms of the alkyl group of the alcohol compound used was 6). Zinc dithiophosphate 2 having a linear alkyl group having 4 carbon atoms and a branched alkyl group having 8 carbon atoms as R ^{3 to} R ^{6 in} a ratio of 2: 2 in the general formula (2) was prepared by the same method as in the production of 1. Synthesized.

<Synthesis of zinc dithiophosphate 3>
In the general formula (2), R ^{3 to} R ⁶ all have carbon atoms by the same method as for the production of zinc dithiophosphate except that 2-ethylhexanol (4.0 mol) was used instead of n-dodecanol. Zinc 3 dithiophosphate, which is a branched alkyl group of 8, was synthesized.

<Amine compound used>
Amine Compound 1: Di-2-ethylhexyl Amine Amine Compound 2: Di-tridecylamine Amine Compound 3: 2-Ethylhexyl Amine

<Compound used in Comparative Example>
Comparative Compound 1: Beef Fat Bis (2-Hydroxyethyl) Amine Comparative Compound 2: Cocobis (2-Hydroxyethyl) Amine Comparative Compound 3: Tri-2-ethylhexylamine Comparative Compound 4: Polyisobutylene Succinimide Comparative Compound 5: Pentaethylene Hexamine Comparative Compound 6: 2-Ethylhexyl Alcohol

<Example 1>
The synthesized zinc dithiophosphate 1 was placed in a 99.9 g flask, 0.1 g of amine compound 1 was added thereto, and the mixture was mixed at 25 ° C. and normal pressure for 10 minutes to produce zinc dithiophosphate (third step). ). At this time, the average carbon number of the alkyl group of the alcohol compound used in the step of synthesizing dithiophosphate is 12, and the average number of carbon atoms of the amine compound used in Example 1 is 8. Therefore, in the step of synthesizing dithiophosphate. The difference between the average carbon number of the alkyl group of the alcohol compound used and the average carbon number of the amine compound used in Example 1 was 4.

<Examples 2 to 18, Comparative Examples 1 to 9>
Zinc dithiophosphates of Examples 2 to 18 and Comparative Examples 1 to 9 were produced by the same method except that the types, addition amounts and mixing conditions of the zinc dithiophosphate and amine compounds used were changed as shown in Table 1. .. In addition, Comparative Examples 1 to 3 represent an example in which an amine compound was not used, and Comparative Examples 4 to 9 represent an example in which a compound other than the amine compound used in the present invention was used.

<Evaluation of odor>
20 mL each of zinc dithiophosphate produced in Examples 1 to 18 and Comparative Examples 1 to 9 was placed in a 100 mL flask, the mouth of the flask was sealed with aluminum foil and rubber ring, and the flask was allowed to stand for 10 minutes in that state. For air, the presence or absence of hydrogen sulfide generation was detected using a hydrogen sulfide detector tube (manufactured by Gastec Co., Ltd .: No. 4LT) under the conditions that the number of suctions was 1 (100 ml) and the suction time was 1.5 minutes. The odorability of this detection result was evaluated according to the following evaluation criteria. If it is ◎ or ○ in this evaluation, it means that there is no practical problem.

<Evaluation criteria for odor>
⊚: Hydrogen sulfide was not detected at all ○: Hydrogen sulfide of less than 0.05 ppm was detected Δ: Hydrogen sulfide of 0.05 or more and less than 0.5 ppm was detected ×: Hydrogen sulfide of 0.5 ppm or more was detected was detected

<Evaluation of extreme pressure>
For the produced zinc dithiophosphate, the maximum non-fused load (LNSL) was measured according to the method described in ASTM D 2596, and the extreme pressure property was evaluated based on each result. Specifically, first, with respect to zinc dithiophosphate of Comparative Examples 1 to 3 (zinc dithiophosphate not subjected to the third step of the present invention), a test ball was subjected to the following conditions using a shell-type high-speed 4-ball tester. The maximum non-fused load (LNSL), which is the load immediately before fusion, was measured. The maximum non-fused load means the load one step before the load in which the test ball is fused when the test is performed by increasing the load on the test ball by 30 kgf (initial load = 30 kgf). .. Next, LNSL was measured for zinc dithiophosphate produced in Examples 1 to 5 and 10 to 13 by the same method. Then, the LNSL value of each zinc dithiophosphate produced in Examples 1 to 5 and 10 to 13 and the LNSL value of zinc dithiophosphate (Comparative Examples 1 to 3) not subjected to the corresponding third step. The extreme pressure was evaluated by comparing the above and evaluating based on the following evaluation criteria. The results are shown in Table 4.

<Test conditions for fusion load>
Rotation speed: 1768 rpm
Measurement time: 10 seconds Measurement temperature: Room temperature

<Evaluation criteria for extreme pressure>
⊚: Same value as the LNSL value of zinc dithiophosphate in which the third step was not performed ◯: 1 to 30 kgf lower than the LNSL value of zinc dithiophosphate in which the third step was not performed Δ: Dithiolin in which the third step was not performed 31 to 60 kgf lower than the LNSL value of zinc acid x: 61 kgf or more lower than the LNSL value of zinc dithiophosphate in which the third step was not performed.

From the above results, it was found that the odor of zinc dithiophosphate obtained by the method of the present invention was improved by a simple method.

Claims (8)

The first step of reacting diphosphorus pentasulfide with an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms, and
In the second step of adding zinc oxide to the product obtained in the first step to neutralize it,
In the third step, the amine compound represented by the following general formula (1) is added to the product obtained in the second step and mixed at 20 to 130 ° C. for 10 minutes to 10 hours.
A method for producing zinc dithiophosphate containing.

(In the formula, R ¹ represents a hydrocarbon group having 4 to 14 carbon atoms, and R ² represents a hydrogen atom or a hydrocarbon group having 4 to 14 carbon atoms). The method for producing zinc dithiophosphate according to claim 1, wherein the amount of the amine compound added is 0.01 to 1.0 parts by mass with respect to 100 parts by mass of the product obtained in the second step. .. The method for producing zinc dithiophosphate according to claim 1 or 2, wherein the alcohol compound contains an alcohol having an alkyl group having 4 to 14 carbon atoms. The production of zinc dithiophosphate according to claim 3, wherein the difference between the average carbon number of the alkyl group of the alcohol compound and the average carbon number of the alkyl group of the amine compound represented by the general formula (1) is 8 or less. Method. A method for improving the odor of zinc dithiophosphate, in which an amine compound represented by the following general formula (1) is added to zinc dithiophosphate and mixed at 20 to 130 ° C. for 10 minutes to 10 hours.

(In the formula, R ¹ represents a hydrocarbon group having 4 to 14 carbon atoms, and R ² represents a hydrogen atom or a hydrocarbon group having 4 to 14 carbon atoms). The zinc dithiophosphate is used in a step of synthesizing dithiophosphate by reacting diphosphorus pentasulfide with an alcohol compound having a hydrocarbon group having 4 to 14 carbon atoms, and by adding zinc oxide to the dithiophosphate. The method for improving the odor of zinc dithiophosphate according to claim 5, which is zinc dithiophosphate synthesized by summing. The method for improving the odor of zinc dithiophosphate according to claim 5 or 6, wherein the amount of the amine compound added is 0.01 to 1.0 part by mass with respect to 100 parts by mass of zinc dithiophosphate. The method for improving the odor of zinc dithiophosphate according to any one of claims 5 to 7, wherein the zinc dithiophosphate is zinc dithiophosphate represented by the following general formula (2).

(In the formula, R ^{3 to} R ⁶ independently represent hydrocarbon groups having 4 to 14 carbon atoms).