WO2023182120A1 - 分散体及び潤滑組成物 - Google Patents

分散体及び潤滑組成物 Download PDF

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WO2023182120A1
WO2023182120A1 PCT/JP2023/010217 JP2023010217W WO2023182120A1 WO 2023182120 A1 WO2023182120 A1 WO 2023182120A1 JP 2023010217 W JP2023010217 W JP 2023010217W WO 2023182120 A1 WO2023182120 A1 WO 2023182120A1
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acid
molybdenum
particles
dispersion
molybdenum disulfide
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PCT/JP2023/010217
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English (en)
French (fr)
Japanese (ja)
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史晃 小寺
佑介 狩野
駿介 山田
浩児 大道
宏尚 松枝
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Dic株式会社
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Priority to JP2024508717A priority Critical patent/JPWO2023182120A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/22—Compounds containing sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives

Definitions

  • the present invention relates to a dispersion formed by dispersing particles of molybdenum disulfide and a lubricating composition containing the same.
  • Molybdenum disulfide (MoS 2 ) is known as a solid lubricant for reducing friction and wear. It is used as one of the paint ingredients.
  • Solid lubricants must be uniformly dispersed in compositions containing them, have excellent dispersion stability over time, and even if sedimentation occurs, they can be redispersed by simple operations. is necessary.
  • Carboxymethyl cellulose, its salts, or glutathione are provided as solid lubricants or dispersants that can be applied to MoS 2 powder (see, for example, Patent Documents 1 and 2).
  • MoS 2 is a crushed product of ore, and contains many particles with a particle size exceeding 1 ⁇ m, and the lubricant effect per weight is small. Therefore, in order to achieve better lubrication performance, it is necessary to make it into fine particles. is necessary. In order to disperse the fine particles in the form of primary particles, further improvements are required as a dispersant.
  • an object of the present invention is to provide a MoS 2 dispersion in which fine MoS 2 capable of exhibiting high lubrication performance is stably dispersed in a liquid medium, and a lubricating composition containing the same.
  • the present invention includes the following aspects.
  • Molybdenum disulfide which has an aspect ratio, which is the ratio between the median diameter D 50 (nm) and the thickness (nm) of the primary particles, is in the range of 2 to 110, and the median diameter D 50 is 100 to 400 nm
  • a dispersion according to [1] wherein the dispersion (B) has two or more linear aliphatic hydrocarbon groups having 4 or more carbon atoms.
  • FIG. 1 is a schematic diagram showing an example of an apparatus used for manufacturing molybdenum trioxide particles, which are the raw material for molybdenum disulfide particles in this embodiment.
  • Molybdenum compounds have conventionally been used as one of solid lubricants.
  • molybdenum disulfide is made into a powder by so-called pulverization, its particle size is large and its specific gravity is as high as about 5. Another problem is that once it settles, it sticks and is difficult to redisperse.
  • engine oil when used in an actual car, etc., after it is poured into an oil tank, it is filtered through an oil filter to remove dust, impurities, precipitates deposited during storage, and other substances that may be generated depending on the use of the engine oil. It is necessary to remove the sludge and protect the sliding parts of the engine. At this time, if the particle size of the solid lubricant is large, or if there are problems such as poor dispersibility and agglomeration, resulting in poor redispersibility, the solid lubricant cannot pass through the filter and the desired lubrication performance is not achieved. There is also the problem that it cannot be expressed over a long period of time.
  • the present invention it is essential to use a specific shape and a minute amount of molybdenum disulfide (A), and specifically, the median diameter D determined by a dynamic light scattering particle size distribution measurement device is 50 is required to be 100 to 400 nm.
  • the particles of molybdenum disulfide (A) have better lubrication performance, that is, even when the friction surfaces of sliding materials are close to each other, they remain without being removed from the gap and continue to maintain lubrication performance.
  • the particle is not perfectly spherical and has an aspect ratio (the ratio of the median diameter D 50 (nm) of the primary particle to the thickness (nm)) of 2 to 110, It is preferably in the range of 2 to 100, particularly preferably in the range of 3 to 90.
  • the thickness used in calculating the aspect ratio can be measured by observation using an atomic force microscope (AFM), and the aspect ratio can be calculated from the measurement results.
  • AFM atomic force microscope
  • the median diameter D50 of the molybdenum disulfide (A) determined by a dynamic light scattering particle size distribution analyzer is 100 to 400 nm, and from the viewpoint of the above-mentioned effects, it is preferably 350 nm or less, more preferably 325 nm or less. , 300 nm or less is particularly preferable.
  • the median diameter D50 of the molybdenum sulfide may be 5 nm or more, or 10 nm or more.
  • the particles of molybdenum disulfide (A) preferably include a 2H crystal structure and a 3R crystal structure of molybdenum disulfide.
  • Molybdenum disulfide which is generally used as a lubricant, has many particles with a particle size exceeding 1 ⁇ m, and is a hexagonal solid lubricant having only a 2H crystal structure.
  • molybdenum disulfide particles produced through the "method for producing molybdenum trioxide particles" and "method for producing molybdenum disulfide particles” described later include a 2H crystal structure and a 3R crystal structure, and have a median diameter D 50 can be easily adjusted.
  • the particles of molybdenum disulfide (A) have a peak around 39.5° and a peak around 49.5° in a spectrum obtained from powder X-ray diffraction (XRD) using Cu-K ⁇ rays as an X-ray source. It is preferable that the peaks around 1° are both synthetic peaks of the 2H crystal structure and 3R crystal structure, and the half width is 1° or more. Furthermore, the particles of molybdenum disulfide (A) may include a crystal structure other than the 2H crystal structure and 3R crystal structure of molybdenum disulfide, such as a 1H crystal structure.
  • the point that the molybdenum disulfide (A) particles include a metastable 3R crystal structure is 39.5 in the spectrum obtained from powder X-ray diffraction (XRD) using Cu-K ⁇ rays as the X-ray source.
  • XRD powder X-ray diffraction
  • the peak around 49.5° and the peak around 49.5° can be distinguished because they both consist of synthetic peaks of the 2H crystal structure and the 3R crystal structure.
  • the shape of the primary particles of the molybdenum disulfide (A) particles in a two-dimensional image taken with a transmission electron microscope (TEM) has an aspect ratio in the range of 2 to 110 as described above, and is plate-shaped, It may be needle-like, string-like, ribbon-like, or sheet-like, or a combination of these shapes may be included.
  • the ribbon-like or sheet-like shape allows the specific surface area of the molybdenum disulfide particles to be increased.
  • the term "ribbon-like" or "sheet-like” refers to a thin layer shape.
  • the shape of the primary particles of the molybdenum disulfide (A) particles is not a simple spherical shape, but a ribbon shape or a sheet shape with a large aspect ratio, so that the friction surfaces of the sliding materials that are about to come into contact with each other are improved. It can be expected that by efficiently covering the surfaces, the probability of contact (or contact area x time) between the friction surfaces of the sliding materials can be reduced, and it is thought that seizure due to rubbing against each other will be less likely to occur.
  • the specific surface area of the molybdenum disulfide (A) particles measured by the BET method is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more, and 40 m 2 /g or more. It is particularly preferable.
  • the specific surface area of the molybdenum sulfide particles measured by the BET method may be 300 m 2 /g or less, 200 m 2 /g or less, or 100 m 2 /g or less.
  • the layers constituting the primary particles approach each other through relatively weak interaction, and the layers can be easily displaced from each other by external force such as friction. Therefore, when the primary particles of the molybdenum disulfide (A) particles are sandwiched between metals that are sliding materials, the layers constituting the primary particles shift due to the frictional force, causing the apparent It is possible to lower the coefficient of friction and also prevent contact between metals that are sliding materials.
  • the intensity I of the peak due to Mo-S and the Mo-Mo is preferably larger than 1.0, more preferably 1.1 or more, particularly preferably 1.2 or more.
  • the crystal structure of molybdenum disulfide is a 2H crystal structure or a 3R crystal structure
  • the distance between Mo-S is almost the same due to the covalent bond, so the extended X-ray absorption fine structure (EXAFS) spectrum of the K absorption edge of molybdenum
  • EXAFS extended X-ray absorption fine structure
  • the intensity of the peak due to Mo-S is the same.
  • the 2H crystal structure of molybdenum disulfide is hexagonal, so the same hexagon is located 90 degrees directly below the hexagon of Mo atoms, so the distance between Mo and Mo becomes close, and Mo and Mo The resulting peak intensity II becomes stronger.
  • the 3R crystal structure of molybdenum disulfide is rhombohedral, so the hexagon is not directly below the hexagon at 90°, but is shifted by half, so the distance between Mo and Mo becomes long, and the Mo -The peak intensity II caused by Mo becomes weaker.
  • the ratio (I/II) becomes small, but as the molybdenum disulfide includes a 3R crystal structure, the ratio (I/II) increases.
  • the hexagons of the Mo atoms in each of the three layers are offset from each other by half a hexagon. It can be expected that the interaction between them will be small and that it will be easier to slip.
  • the molybdenum disulfide (A) can be produced, for example, by heating molybdenum trioxide particles having an average primary particle diameter of 5 to 1000 nm at a temperature of 300 to 800° C. in the presence of a sulfur source.
  • the average particle diameter of the primary particles of molybdenum trioxide particles is the smallest particle size that constitutes an aggregate on a two-dimensional image of molybdenum trioxide particles photographed with a scanning electron microscope (SEM) or transmission electron microscope (TEM).
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the average value is the primary particle diameter of 50 randomly selected primary particles.
  • the molybdenum oxide particles used in the production of molybdenum disulfide (A) are preferably composed of an aggregate of primary particles containing a ⁇ crystal structure of molybdenum trioxide.
  • the molybdenum oxide particles have better reactivity with sulfur than conventional molybdenum trioxide particles that have only ⁇ crystals as a crystal structure, and contain the ⁇ crystal structure of molybdenum trioxide, so they are less reactive with sulfur sources. In this case, the conversion rate R C to MoS 2 can be increased.
  • the ⁇ crystal structure of molybdenum trioxide is (2 ⁇ : This can be confirmed by the presence of a peak of No. 86426 (Inorganic Crystal Structure Database (ICSD)) near 23.01°.
  • the ⁇ crystal structure of molybdenum trioxide can be confirmed by the presence of a peak on the (021) plane (2 ⁇ : around 27.32°, No. 166363 (Inorganic Crystal Structure Database (ICSD)) of the ⁇ crystal of MoO 3 I can do it.
  • sulfur source examples include sulfur, hydrogen sulfide, etc., and these may be used alone or in combination of two types.
  • the method for producing molybdenum disulfide (A) includes heating molybdenum trioxide particles consisting of an aggregate of primary particles containing a ⁇ -crystalline structure of molybdenum trioxide at a temperature of 200 to 800°C in the absence of a sulfur source; Next, it may include heating at a temperature of 200 to 1000° C. in the presence of a sulfur source.
  • the heating time in the presence of the sulfur source may be any time as long as the sulfurization reaction sufficiently proceeds, and may be 1 to 20 hours, 2 to 15 hours, or 3 to 10 hours. Good too.
  • the charging ratio of the amount of S in the sulfur source to the amount of MoO 3 in the molybdenum trioxide particles is preferably such that the sulfurization reaction sufficiently proceeds.
  • the amount of S in the sulfur source is preferably 250 mol% or more, preferably 400 mol% or more, and preferably 500 mol% or more with respect to 100 mol% MoO 3 of the molybdenum trioxide particles. is preferred.
  • the amount of S in the sulfur source may be 3000 mol% or less, 2000 mol% or less, or 1500 mol% or less with respect to 100 mol% MoO 3 of the molybdenum trioxide particles. Good too.
  • the heating temperature in the presence of the sulfur source may be any temperature at which the sulfurization reaction sufficiently proceeds, and is preferably 320°C or higher, and preferably 340°C or higher. It is more preferable that the temperature is 360° C. or higher.
  • the temperature may be 320 to 1000°C, 340 to 1000°C, or 360 to 600°C.
  • the average particle size of the primary particles of the molybdenum trioxide particles is preferably 1 ⁇ m or less.
  • the diameter is more preferably 600 nm or less, even more preferably 400 nm or less, and particularly preferably 200 nm or less.
  • the average particle size of the primary particles of the molybdenum trioxide particles may be 10 nm or more, 20 nm or more, or 40 nm or more.
  • the molybdenum trioxide particles have a MoO 3 content of 99.6% or more as measured by X-ray fluorescence (XRF).
  • XRF X-ray fluorescence
  • the molybdenum trioxide particles are characterized in that the molybdenum trioxide particles (The ratio ( ⁇ (011)/ ⁇ (021)) of the peak intensity attributable to the (011) plane to the peak intensity attributable to the (021) plane of the ⁇ crystal of MoO 3 is preferably 0.1 or more.
  • the peak intensity attributable to the (011) plane of the ⁇ crystal of MoO 3 and the peak intensity attributable to the (021) plane of the ⁇ crystal of MoO 3 are calculated by reading the maximum intensity of the peak and calculating the ratio ( ⁇ (011) )/ ⁇ (021)).
  • the ratio ( ⁇ (011)/ ⁇ (021)) is preferably 0.1 to 10.0, more preferably 0.2 to 10.0, and 0. A range of .4 to 10.0 is particularly preferred.
  • the molybdenum trioxide particles preferably have a specific surface area of 10 m 2 /g to 150 m 2 /g as measured by the BET method.
  • the specific surface area is preferably 10 m 2 /g or more, preferably 20 m 2 /g or more, and 30 m 2 /g because the reactivity with sulfur becomes good. It is preferable that it is above.
  • the particle size is preferably 120 m 2 /g or less, may be 100 m 2 /g or less, or may be 80 m 2 /g or less, since manufacturing becomes easy.
  • the molybdenum trioxide particles have an intensity I of a peak due to Mo-O and a peak due to Mo-Mo in a radial distribution function obtained from an extended X-ray absorption fine structure (EXAFS) spectrum at the K absorption edge of molybdenum. It is preferable that the ratio (I/II) to intensity II is greater than 1.1.
  • the ratio (I/II) is considered to be an indicator that the ⁇ crystal structure of MoO 3 is obtained in the molybdenum trioxide particles, and the larger the ratio (I/II), the greater the reactivity with sulfur. Excellent in
  • the ratio (I/II) is preferably 1.1 to 5.0, may be 1.2 to 4.0, and may be 1.2 to 3.0. There may be.
  • the molybdenum trioxide particles can be produced by vaporizing a molybdenum oxide precursor compound to form molybdenum trioxide vapor and cooling the molybdenum trioxide vapor.
  • the method for producing molybdenum trioxide particles includes firing a raw material mixture containing a molybdenum oxide precursor compound and a metal compound other than the molybdenum oxide precursor compound, vaporizing the molybdenum oxide precursor compound, and producing molybdenum trioxide particles. It is preferable that the proportion of the metal compound is 70% by mass or less in terms of oxide, based on 100% by mass of the raw material mixture, including forming steam.
  • the method for producing molybdenum trioxide particles can be suitably carried out using the production apparatus 1 shown in FIG.
  • FIG. 1 is a schematic diagram of an example of an apparatus used for producing the molybdenum trioxide particles.
  • the manufacturing apparatus 1 includes a firing furnace 2 for firing a molybdenum oxide precursor compound or the raw material mixture and vaporizing the molybdenum oxide precursor compound, and a firing furnace 2 for firing molybdenum trioxide vaporized by the firing. It has a cross-shaped cooling pipe 3 that turns steam into particles, and a recovery machine 4 that is a recovery means for collecting molybdenum trioxide particles that have been turned into particles in the cooling pipe 3. At this time, the firing furnace 2 and the cooling pipe 3 are connected via the exhaust port 5.
  • the cooling pipe 3 has an opening adjustment damper 6 disposed at an outside air intake port (not shown) at the left end thereof, and an observation window 7 at the upper end thereof.
  • the manufacturing apparatus 1 may include an external cooling device 9, thereby making it possible to arbitrarily control the cooling conditions of the molybdenum trioxide vapor generated from the firing furnace 2.
  • the opening adjustment damper 6 takes in air from the outside air intake port, cools the molybdenum trioxide vapor vaporized in the firing furnace 2 in an air atmosphere, and converts it into molybdenum trioxide particles, thereby achieving the ratio (I/II).
  • the ratio (I/II) can be made larger than 1.1, and the ⁇ crystal structure of MoO 3 can be easily obtained in the molybdenum trioxide particles. Cooling molybdenum trioxide vapor in a state where the oxygen concentration is low in a nitrogen atmosphere, such as when molybdenum trioxide vapor is cooled using liquid nitrogen, increases the oxygen defect density and lowers the ratio (I/II). Easy to lower.
  • molybdenum oxide precursor compound a precursor compound for forming molybdenum trioxide particles consisting of an aggregate of primary particles containing a ⁇ crystal structure of molybdenum trioxide is preferable.
  • the molybdenum oxide precursor compound is not particularly limited as long as it forms molybdenum trioxide vapor when fired, and examples thereof include metal molybdenum, molybdenum trioxide, molybdenum dioxide, molybdenum sulfide, and the like.
  • the molybdenum oxide precursor compound it is preferable to use commercially available ⁇ -crystalline molybdenum trioxide.
  • ammonium molybdate is used as the molybdenum oxide precursor compound, it is converted into thermodynamically stable molybdenum trioxide by calcination, so the molybdenum oxide precursor compound that is vaporized becomes the molybdenum trioxide. .
  • Molybdenum trioxide vapor can also be formed by firing a raw material mixture containing a molybdenum oxide precursor compound and a metal compound other than the molybdenum oxide precursor compound.
  • Metal compounds other than the molybdenum oxide precursor compound are not particularly limited, but include aluminum compounds, silicon compounds, titanium compounds, magnesium compounds, sodium compounds, potassium compounds, zirconium compounds, yttrium compounds, zinc compounds, copper compounds, and iron compounds. etc. Among these, it is preferable to use aluminum compounds, silicon compounds, titanium compounds, and magnesium compounds.
  • the molybdenum oxide precursor compound and a metal compound other than the molybdenum oxide precursor compound may form an intermediate, but even in this case, the intermediate decomposes during calcination, making molybdenum trioxide thermodynamically stable. It can be vaporized in the form.
  • the metal compound other than the molybdenum oxide precursor compound it is preferable to use an aluminum compound to prevent damage to the firing furnace, and to improve the purity of the molybdenum trioxide particles, it is preferable to use an aluminum compound. It is also possible not to use a metal compound other than the compound.
  • Examples of aluminum compounds include aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum hydroxide, boehmite, pseudoboehmite, aluminum transition oxides ( ⁇ -aluminum oxide, ⁇ -aluminum oxide, ⁇ -aluminum oxide, etc.), Examples include ⁇ -aluminum oxide, aluminum mixed oxide having two or more types of crystal phases, and the like.
  • the content ratio of the molybdenum oxide precursor compound with respect to 100% by mass of the raw material mixture is 40% to 100%. %, and may be from 45% to 100%, or from 50% to 100%.
  • the firing temperature varies depending on the molybdenum oxide precursor compound, metal compound, and desired molybdenum trioxide particles used, it is usually preferable to set the temperature at which the intermediate can be decomposed.
  • the temperature at which the intermediate can be decomposed is usually 500°C to 1500°C. , more preferably 600°C to 1550°C, even more preferably 700°C to 1600°C.
  • the firing time is also not particularly limited, and can be, for example, 1 minute to 30 hours, 10 minutes to 25 hours, or 100 minutes to 20 hours.
  • the temperature increase rate varies depending on the molybdenum oxide precursor compound used, the metal compound, and the desired characteristics of the molybdenum trioxide particles, but from the viewpoint of production efficiency, it should be 0.1 to 100 ° C./min.
  • the rate is preferably 1 to 50°C/min, more preferably 2 to 10°C/min.
  • the internal pressure in the firing furnace is not particularly limited and may be positive pressure or reduced pressure, but from the viewpoint of discharging the molybdenum oxide precursor compound from the firing furnace to the cooling piping, firing is performed under reduced pressure. It is preferable that the process be carried out in The specific degree of reduced pressure is preferably -5000 to -10 Pa, more preferably -2000 to -20 Pa, and even more preferably -1000 to -50 Pa. It is preferable that the degree of reduced pressure is ⁇ 5000 Pa or higher because the firing furnace does not require excessively high airtightness or mechanical strength, and manufacturing costs can be reduced. On the other hand, it is preferable that the degree of reduced pressure is -10 Pa or less, since clogging of the molybdenum oxide precursor compound at the outlet of the firing furnace can be prevented.
  • the temperature of the blown gas is preferably 5 to 500°C, more preferably 10 to 100°C.
  • the gas blowing speed is preferably 1 to 500 L/min, more preferably 10 to 200 L/min, based on the effective volume of the firing furnace of 100 L.
  • the temperature of the vaporized molybdenum trioxide vapor varies depending on the type of molybdenum oxide precursor compound used, but is preferably 200 to 2000°C, more preferably 400 to 1500°C. Note that if the temperature of the vaporized molybdenum trioxide vapor is 2000° C. or lower, it tends to be easily turned into particles by blowing outside air (0 to 100° C.) in the cooling pipe.
  • the discharge rate of molybdenum trioxide vapor discharged from the firing furnace depends on the amount of the molybdenum oxide precursor compound used, the amount of the metal compound, the temperature of the firing furnace, the blowing of gas into the firing furnace, and the diameter of the firing furnace exhaust port. It can be controlled by Although it varies depending on the cooling capacity of the cooling pipe, the discharge rate of molybdenum trioxide vapor from the firing furnace to the cooling pipe is preferably 0.001 to 100 g/min, and preferably 0.1 to 50 g/min. More preferred.
  • the content of molybdenum trioxide vapor contained in the gas discharged from the firing furnace is preferably 0.01 to 1000 mg/L, more preferably 1 to 500 mg/L.
  • the molybdenum trioxide vapor is cooled and turned into particles.
  • Molybdenum trioxide vapor is cooled by lowering the temperature of the cooling piping.
  • the cooling means include cooling by blowing gas into the cooling pipe, cooling by a cooling mechanism included in the cooling pipe, cooling by an external cooling device, etc. as described above.
  • the molybdenum trioxide vapor is preferably cooled under an air atmosphere.
  • the ratio (I/II) can be made larger than 1.1, and in the molybdenum trioxide particles, ⁇ crystals of MoO 3 Structure is easy to obtain.
  • the cooling temperature (temperature of the cooling pipe) is not particularly limited, but is preferably -100 to 600°C, more preferably -50 to 400°C.
  • the cooling rate of molybdenum trioxide vapor is not particularly limited, but is preferably 100 to 100,000°C/s, more preferably 1,000 to 50,000°C/s. Note that the faster the cooling rate of the molybdenum trioxide vapor, the more molybdenum trioxide particles tend to be obtained with a smaller particle size and a larger specific surface area.
  • the temperature of the blowing gas is preferably -100 to 300°C, more preferably -50 to 100°C.
  • the gas blowing speed is preferably 0.1 to 20 m 3 /min, more preferably 1 to 10 m 3 /min. It is preferable that the gas blowing speed is 0.1 m 3 /min or more because a high cooling speed can be achieved and clogging of the cooling pipe can be prevented. On the other hand, it is preferable that the gas blowing speed is 20 m 3 /min or less because an expensive first blowing means (exhaust fan, etc.) is not required, and manufacturing costs can be reduced.
  • the particles obtained by cooling the molybdenum trioxide vapor are transported to a recovery machine and recovered.
  • particles obtained by cooling the molybdenum trioxide vapor may be fired again at a temperature of 100° C. to 320° C.
  • the molybdenum trioxide particles obtained by the method for producing molybdenum trioxide particles may be fired again at a temperature of 100° C. to 320° C.
  • the firing temperature for the second firing may be 120°C to 280°C, or 140°C to 240°C.
  • the firing time for the second firing can be, for example, 1 minute to 4 hours, 10 minutes to 5 hours, or 100 minutes to 6 hours.
  • a part of the ⁇ crystal structure of molybdenum trioxide disappears, and when fired at a temperature of 350°C or higher for 4 hours, the ⁇ crystal structure in the molybdenum trioxide particles disappears.
  • molybdenum trioxide particles suitable for producing the molybdenum sulfide particles can be produced.
  • Dispersion in this embodiment uses a dispersant (B) having a linear aliphatic hydrocarbon group having 4 or more carbon atoms.
  • the dispersant (B) is effectively disposed between the liquid medium (C) described later and the molybdenum disulfide (A), resulting in improved dispersibility. is good, and even if the molybdenum disulfide (A) particles contact each other, strong adhesion does not occur and redispersibility is also good. As a result, it has good oil filter permeability and can exhibit stable lubrication performance over a long period of time.
  • the dispersant contains one or more linear aliphatic hydrocarbon groups having 4 or more carbon atoms, but it may contain two or more. In particular, when the number of carbon atoms is 4, it is preferable to have 2 or more carbon atoms in the molecule.
  • the linear aliphatic hydrocarbon group may have a methyl group having 1 carbon atom as a substituent, but molybdenum disulfide is linear and has 4 or more carbon atoms connected to each other. (A) is likely to exhibit its inherent effects such as lubrication performance.
  • the number of linear carbon atoms is preferably 8 or more, and preferably 28 or less, that is, the number of carbon atoms is preferably in the range of 4 to 28, and is in the range of 8 to 28. and more preferable.
  • the dispersion of this embodiment is used particularly as a lubricating composition, etc., from the viewpoint of further increasing the affinity with the liquid medium (C) described later, it is preferable to use unsaturated aliphatic hydrocarbon groups in the aliphatic hydrocarbon group It is preferable to have one or more bonds (carbon-carbon double bond).
  • the unsaturated bond may have two or more, and although it depends on the number of carbon atoms, it is preferably six or less.
  • the dispersant (B) preferably contains one or more heteroatoms in its structure from the viewpoint of further increasing the affinity with molybdenum disulfide (A).
  • the heteroatom is not particularly limited, but is preferably a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, particularly preferably a nitrogen atom, a sulfur atom, or a phosphorus atom. Most preferably.
  • Examples of the method for introducing the nitrogen atom into the dispersant (B) include a method of reacting an amine compound with an alkyl halide, alcohol, acid anhydride, epoxy compound, etc. to disperse oxygen atoms.
  • a method for introducing the compound into the agent (B) a general esterification reaction or using an epoxy compound as a raw material and reacting various compounds with the epoxy group can be used as appropriate.
  • a commercially available compound having a long-chain aliphatic hydrocarbon group may be used as is. These compounds may be used alone as the dispersant (B), or two or more kinds may be used in combination.
  • dispersant (B) having a sulfur atom and the dispersant (B) having a phosphorus atom commercially available disulfide compounds and phosphoric acid compounds can be used as they are or after various modifications.
  • Examples of compounds having a sulfur atom that can be used as the dispersant (B) in the present invention include disulfides having a linear hydrocarbon having 4 or more carbon atoms, and thiol compounds having 4 or more carbon atoms. It will be done.
  • Examples of compounds that have a phosphorus atom and can be used as the dispersant (B) in the present invention include phosphoric ester compounds that have a linear hydrocarbon having 4 or more carbon atoms. At this time, monoesters and diesters are preferable, and monoesters are more preferable, from the viewpoint of further improving the effects of the present invention.
  • the weight average molecular weight is preferably 40,000 or less, more preferably 30,000 or less, particularly preferably 25,000 or less, and most preferably 20,000 or less.
  • This weight average molecular weight is a value measured by the measurement method (GPC) described in the example when the resin has a molecular weight distribution, and when it is composed of a single compound, it is calculated from the raw material and reaction route. molecular weight.
  • Such a dispersant (B) may consist of a single compound, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the average molecular weight is within the above range.
  • the proportion of the dispersant (B) to be used is not particularly limited as long as molybdenum disulfide (A) can be suitably dispersed, but is 10 to 10 parts by mass per 100 parts by mass of the molybdenum disulfide (A).
  • a content in the range of 500 parts by mass is preferred from the viewpoint of easy balance between dispersibility and lubricating performance, and a range of 20 to 200 parts by mass is particularly preferred.
  • Particularly suitable dispersants (B) include, for example, commercially available products such as octylamine, decylamine, tetradecylamine, hexadecylamine, eicosylamine, dodecenylamine, hexadecenylamine, and octadecenylamine.
  • octadecadienylamine stearylamine, palmitylamine, oleylamine, linoleylamine, linolenylamine, 9,12-octadecadienylamine (linolamine), laurylamine, 9,12,15-octadecatrienylamine , dibutylamine, dihexylamine, monooleyltrimethylammonium chloride, dioleyldimethylammonium chloride, polyalkyleneoxymonomethyldioleylammonium chloride, bis(polyalkyleneoxy)monomethylmonooleyl ammonium chloride, oleylglycerin ester, stearylglycerin ester, laurylglycerin Ester compounds such as esters, amide compounds such as laurylamide, oleylamide, and stearylamide, phosphoric acid compounds such as oleyl phosphate and propyl phosphate,
  • decanethiol dodecanethiol, hexadecanethiol, nonanethiol, octadecanethiol, octanethiol, pentadecanethiol, tetradecanethiol, decanethiol, undecanethiol, dodecanethiol, mercaptoundecyl trifluoroacetate, 1H, 1H, 2H, 2H- Thiol compounds such as perfluorodecanethiol, 2-ethylhexanethiol, cis-9-octadecene-1-thiol, tert-dodecylmercaptan, tert-nonylmercaptan, 9-9-octadecentiol, 9E-9-1-butylthio
  • Examples include thio compounds such as -9-octadecene and di-2E-2-buten
  • a compound obtained by reacting a relatively low molecular weight amine compound with a long chain fatty acid can also be suitably used.
  • amine compounds that can be used at this time include pentamethylene diamine, hexamethylene diamine, m-xylylene diamine, p-xylylene diamine, isophorone diamine, bis(aminomethyl)cyclohexane, bis(aminocyclohexyl)methane, 2,5-bis(aminomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(aminomethyl)bicyclo-[2.2.1]-heptane, tolylenediamine, 4,4' - Diamine compounds such as diphenylmethanediamine and phenylenediamine are mentioned.
  • alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine may be used.
  • This amine compound includes straight chain fatty acids such as caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, and arachidic acid.
  • acids linear monoenoic acids such as pentadecenoic acid, hexedenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, oleic acid, nonadecenoic acid, gondotic acid; methylheptenoic acid, methylnonenoic acid, methylundecenoic acid, dimethyldecenoic acid, methyldodecenoic acid Branched monoenoic acids such as , methyl tridecenoic acid, dimethyl dodecenoic acid, dimethyl tridecenoic acid, methyl octadecenoic acid, dimethyl heptadecenoic acid, ethyl octadecenoic acid; linoleic acid, linoleaidic acid, eleostearic acid, linolenic acid.
  • linear monoenoic acids such as pentadecenoic acid, hexedenoic
  • acids di- or trienoic acids such as linolenic acid, pseudoeleostearic acid, parinaric acid, arachidonic acid; octic acid, nonic acid, decynic acid, undecic acid, dodecic acid, tridecic acid, tetradecic acid, pentadecic acid, Acetylenic acids such as heptadecynic acid, octadecynoic acid, nonadecynoic acid, dimethyloctadecenoic acid; methylene octadecenoic acid, methylene octadecanoic acid, alleprolic acid, areprestic acid, alleprylic acid, arepuric acid, hydronocarponic acid, Schollmooglic acid,
  • the desired dispersant can be obtained by reacting fatty acids such as cyclic acids such as gol phosphoric acid, ⁇ -cyclopentylic acid, ⁇ -cyclohexylic acid, and ⁇
  • Isocyanate compounds that can be used at this time include, for example, aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate , isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and other alicyclic diisocyanate compounds; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4' Examples include aromatic diis
  • the compound obtained by reacting the above-mentioned fatty acid with the epoxy group in the epoxy compound contains a hydroxyl group, an ether bond, and an ester bond due to the ring-opening reaction of the epoxy group, which improves the dispersion effect. Therefore, it is a preferred dispersant.
  • epoxy compound a compound with a relatively low molecular weight can be used alone, or a mixture of compounds having a plurality of different skeletons can be used as an epoxy resin containing a compound with a different number of repeats.
  • Commercially available epoxy resins include, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, polyhydroxybenzene epoxy resin, polyhydroxynaphthalene epoxy resin, and biphenyl epoxy resin.
  • Epoxy resin liquid epoxy resin such as tetramethylbiphenyl type epoxy resin, brominated epoxy resin such as brominated phenol novolac type epoxy resin, solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, bisphenol F novolac type epoxy resin, cresol Novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol Novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl-modified novolac type epoxy resin etc., and may be used alone or in combination of two or
  • the reaction between these epoxy resins and the fatty acids may be carried out by any known method and is not particularly limited. Further, a part of the raw material may remain in the obtained reaction product, or it may be purified into a single compound and then used as the dispersant (B).
  • compounds obtained by reacting a monofatty acid with a low molecular weight amine compound, and compounds obtained by reacting a monofatty acid with a low molecular weight isocyanate compound are used. It is preferable to use a compound obtained by reacting a low molecular weight epoxy resin with a monofatty acid.
  • the dispersion in this embodiment contains a liquid medium (C). That is, the dispersion in this embodiment is obtained by dispersing the molybdenum disulfide (A) described above in the liquid medium (C) using the dispersant (B).
  • the liquid medium (C) may be, for example, solid at room temperature or liquefied by heating, and may include water, various organic solvents, oils and fats, liquid resins (thermoplastic resins, etc.). ) or a mixture thereof, and can be appropriately selected depending on the intended use.
  • oil or fat when used as a liquid medium, it can be suitably used as a lubricating composition as described below.
  • an organic solvent when used, it can be suitably used in paints based on molybdenum disulfide (A).
  • the paint is made by dispersing molybdenum disulfide in a binder solution in which a binder resin is dissolved in a solvent.
  • the binder resin include polyamideimide, epoxy resin, furan resin, melamine resin, acrylic resin, and urethane resin.
  • solvents include xylene, toluene, butanol, isobutyl alcohol, isopropyl alcohol, dioxane, methyl ethyl ketone, and n-methyl-2-pyrrolidone.
  • antifoaming agents, stabilizers, flame retardants, curing accelerators, pigments, etc. may be appropriately added to the paint. .
  • various solvents can be selected, such as alcohol-based, ketone-based, hydrocarbon-based, glycol-based, and water-based.
  • alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone;
  • Ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; amides
  • liquid resin monomers or oligomers that are cured by polymerization such as methyl methacrylate or styrene, thermoplastic resins, etc. dissolved in organic solvents, reactive monomers, etc.
  • thermoplastic resins they become fluid at temperatures above their melting point, so by considering the heat resistance aspect of the dispersant (B) mentioned above, this method can be used without using it in combination with other liquid media. It is also possible to use it as the liquid medium (C) of the dispersion in the embodiments.
  • plasticizers such as triethylene glycol di-2-ethyl hexaonate, triethylene glycol di-2-ethyl butyrate, and tetraethylene glycol di-2-ethyl hexaonate that can be used with these resins. It can also be used when dispersing molybdenum disulfide (A).
  • the lubricating composition of this embodiment can be obtained by using base oil that is mineral oil, synthetic oil, or partially synthetic oil as the liquid medium (C).
  • Base oils that are mineral oils include oils obtained by rock drilling, oils obtained from plants or animals, and mixtures thereof, such as, for example, castor oil, lard oil, olive oil, Examples include, but are not limited to, peanut oil, corn oil, soybean oil, linseed oil, liquid petroleum oil, and base oils of the paraffinic, naphthenic, or paraffinic-naphthenic type. Such base oils may be partially or fully hydrogenated if desired.
  • base oils that are synthetic oils include polyalphaolefin-based, hydrocarbon-based, ester-based, ether-based, silicone-based, alkylnaphthalene-based, and perfluoroalkyl polyether-based base oils.
  • Base oil that is partially synthetic oil refers to base oil that is a mixture of these mineral oils and synthetic oils.
  • any base oil generally used for lubricating compositions can be used without limitation.
  • the kinematic viscosity at 40° C. of the base oil used in the lubricating composition of this embodiment may be 10 to 1000 mm 2 /s, 20 to 500 mm 2 /s, or 30 to 200 mm 2 /s.
  • the speed may be 40 to 150 mm 2 /s.
  • the median diameter D50 of the molybdenum disulfide particles determined by a dynamic light scattering particle size distribution analyzer is as small as 100 to 400 nm, by using the dispersant (B) in combination, Even if a base oil with relatively low viscosity is used, sedimentation of molybdenum disulfide particles can be suppressed.
  • the lubricating composition preferably contains 0.0001% by mass to 50% by mass of molybdenum disulfide (A), which is the lubricant, based on 100% by mass of the total mass of the lubricating composition, and 0.01% by mass. % to 10% by mass, and particularly preferably 0.1% to 5% by mass.
  • A molybdenum disulfide
  • the lubricating composition may further contain known additives such as detergents, viscosity modifiers, foam inhibitors, corrosion inhibitors, rust inhibitors, antioxidants, anti-wear agents and friction modifiers. can.
  • liquid medium (C) used at this time a known base oil
  • a known base oil can be used as the liquid medium (C) used at this time.
  • a known base oil can be used as the liquid medium (C) used at this time.
  • a known base oil can be used as the liquid medium (C) used at this time.
  • naphthenic and/or paraffinic mineral oils spindle oil, turbine oil, motor oil, bright stock, etc.
  • synthetic oils diester, polyol ester, silicone oil, PFPE (perfluoropolyether), PAO (polyalphaolefin) , PAG (polyalkylene glycol), alkyldiphenyl ether, polyphenyl ether, and the like.
  • soap-based or non-soap-based thickeners can be used.
  • the soap-based soap include one or more selected from Ca soap (beef tallow-based or castor oil-based), Li complex soap, Ba complex soap, Al soap, Ca complex, Li complex, Al complex, and the like.
  • the non-soap type include urea compounds (one or more selected from aromatic diurea, aliphatic or alicyclic diurea, triurea, tetraurea, Na terephthalate, PTFE, bentonite, silica gel, carbon black, etc.) .
  • the particle-containing grease composition when used as the particle-containing grease composition, it may further contain a load-bearing additive from the viewpoint of reducing frictional wear between frictional surfaces and preventing seizure.
  • a load-bearing additive include one or more selected from Pb naphthenate, chlorinated paraffin, SP type, various metal compounds, phosphorus type and sulfur type compounds such as MoDTP and ZnDTP, and the like.
  • the proportion of molybdenum disulfide (A) used in the dispersion according to the present embodiment can be set as appropriate depending on the intended use and the level of effect.
  • the amount of molybdenum (A) is 0.003 to 0.3 parts by mass, preferably 0.001 to 0.1 parts by mass.
  • the method for producing the dispersion according to this embodiment is not particularly limited, and includes uniformly mixing molybdenum disulfide particles (A), dispersant (B), and liquid medium (C). It can be manufactured by Further, other additives may be further added and mixed uniformly as necessary. A method may be used in which molybdenum disulfide (A) and the dispersant (B) are mixed in advance to form a paste, and then this is mixed with the liquid medium (C).
  • the mixture of the molybdenum disulfide (A) in a pasty state and the dispersion (B) can be mixed with a Hoover Muller, a rotation-revolution kneader, or a three-way kneader.
  • Uniform dispersion can be achieved by kneading with the liquid medium (C) using a roll mill, shallot colloid mill, Monton-Gorlin homogenizer, or the like.
  • Specific surface area measurement A sample of molybdenum trioxide particles or molybdenum disulfide particles is measured with a specific surface area meter (BELSORP-mini manufactured by Microtrack Bell), and the surface area per 1 g of the sample is determined from the amount of nitrogen gas adsorbed by the BET method. It was calculated as specific surface area (m 2 /g).
  • R C (%) (I A /K A )/( ⁇ (I B /K B )) ⁇ 100...(1)
  • ISD Inorganic Crystal Structure Database
  • PDXL integrated powder X-ray analysis software
  • EXAFS Extra X-ray absorption fine structure
  • Synthesis example 1 Molybdenum trioxide was produced using an RHK simulator (manufactured by Noritake Co., Ltd.) as a firing furnace and a VF-5N dust collector (manufactured by Amano Corporation) as a dust collector. 1.5 kg of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.) and 1 kg of molybdenum trioxide (manufactured by Nippon Inuki Co., Ltd.) were mixed, then placed in a pod and fired at a temperature of 1100° C. for 10 hours. During firing, outside air (blow speed: 150 L/min, outside air temperature: 25° C.) was introduced from the side and bottom surfaces of the firing furnace. After molybdenum trioxide was evaporated in the furnace, it was cooled near the dust collector and precipitated as particles, so molybdenum trioxide (1) was collected using the dust collector.
  • RHK simulator manufactured by Noritake Co., Ltd.
  • molybdenum trioxide (1) After firing, 1.0 kg of aluminum oxide as a blue powder and 0.8 kg of molybdenum trioxide (1) collected by a dust collector were taken out from the pod.
  • the recovered molybdenum trioxide (1) had a primary particle median diameter D 50 of 87.8 nm as determined by dynamic light scattering, and the particle shape observed by TEM was ribbon or particulate. Fluorescent X-ray measurement confirmed that the purity of molybdenum trioxide (1) (MoO 3 content) was 99.9% by mass.
  • the content of ⁇ crystals of molybdenum trioxide can be determined from the obtained profile data by the RIR (Reference Intensity Ratio) method.
  • the content (%) of ⁇ crystals of molybdenum trioxide can be determined from the following equation (2).
  • Content of alpha crystals of molybdenum trioxide (%) (IA/KA)/((IA/KA)+(IB/KB)) ⁇ 100...(2)
  • the values listed in the ICSD database can be used as the RIR values, and integrated powder X-ray analysis software (manufactured by Rigaku, PDXL Version 2) can be used for analysis.
  • the content of ⁇ -crystals of molybdenum trioxide determined from formula (2) was 30%.
  • Synthesis example 2 In a magnetic crucible, 100 g of the molybdenum trioxide particles obtained in Synthesis Example 1 and 112 g of sulfur powder (manufactured by Kanto Kagaku) were mixed with a stirring bar so that the powder was uniform, and the mixture was heated in a high-temperature atmosphere firing furnace. The inside of the furnace was evacuated and replaced with nitrogen, and firing was performed at 500° C. for 4 hours in a nitrogen atmosphere to obtain a black powder.
  • the S amount of the sulfur is 500 mol% with respect to the MoO 3 amount of the molybdenum trioxide, which is 100 mol%.
  • Example 1 After accurately weighing 1 g of molybdenum disulfide (A-1) obtained in Synthesis Example 2 and 2 g of oleylamine purchased from Tokyo Chemical Industry Co., Ltd. as a dispersant (B-1) into a 10 ml vial, use a spatula to prepare a reserve. Mixed. Thereafter, the mixture was kneaded for 1 minute using a Hoover muller manufactured by Toyo Seiki Seisakusho under a load of 4 kg to obtain a paste of molybdenum disulfide.
  • the obtained dispersion 1 was allowed to stand at room temperature (25° C.) for 1000 hours, and sedimentation was confirmed. The results are shown in Table 2.
  • the amount of sedimentation was expressed as a sedimentation score. The closer the score is to 5, the lower the amount of sedimentation generated.
  • Score 0 The amount of sedimentation is greater than Comparative Example 1, which will be described later.
  • Score 1 The amount of sedimentation is at the same level as Comparative Example 1.
  • Score 2 The amount of sedimentation is less than Comparative Example 1, but the amount of sedimentation increases over time.
  • Score 3 Slight sedimentation occurs during the test
  • Score 4 Slight sedimentation occurs at the end of the test
  • Score 5 Almost no sedimentation occurs throughout the test
  • Synthesis Example 3 Synthesis method of dispersant (B-2) 201 parts by mass of propylene glycol monomethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 201 parts by mass of propylene glycol monomethyl ether acetate was added to the bisphenol F novolak type epoxy resin "EPICLON N". -570'' (manufactured by DIC Corporation, softening point 69°C, epoxy equivalent: 187 g/eq) was dissolved, 0.9 parts by mass of dibutylhydroxytoluene was added, and 282 parts by mass of oleic acid and triphenyl were dissolved. 2.3 parts by mass of phosphine was added and the reaction was carried out at 120° C. for 10 hours in a nitrogen atmosphere to obtain a dispersant (B-2). The weight average molecular weight of the obtained dispersant was 18,760.
  • Synthesis Example 4 Synthesis method of dispersant (B-3) 203 parts by mass of propylene glycol monomethyl ether acetate was put into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and 203 parts by mass of propylene glycol monomethyl ether acetate was added to the bisphenol F novolak type epoxy resin "EPICLON N". -570H'' (manufactured by DIC Corporation, softening point 80°C, epoxy equivalent: 191 g/eq) was dissolved, and 0.9 parts by mass of dibutylhydroxytoluene was added, followed by 282 parts by mass of oleic acid and triphenyl. 2.4 parts by mass of phosphine was added and the reaction was carried out at 120° C. for 10 hours in a nitrogen atmosphere to obtain a dispersant (B-3). The weight average molecular weight of the obtained dispersant was 24,250.
  • Synthesis Example 5 Synthesis method of dispersant (B-4) 342 parts by mass of diethylene glycol monoethyl ether acetate and 222 parts by mass of isophorone diisocyanate were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dibutyl hydroxy After adding 1.6 parts by mass of toluene, 564 parts by mass of oleic acid was added, and the reaction was carried out at 180°C for 15 hours in a nitrogen atmosphere. After confirming that the NCO% was 0.1 or less, the dispersion was performed. Agent (B-4) was obtained. The weight average molecular weight of the obtained dispersant was 1,370.
  • Example 2-20 In the same manner as in Example 1 except that the dispersant and liquid medium were changed, the settling properties after 1000 hours were confirmed using various dispersants. The results are shown in Table 2.
  • Comparative example 1 After accurately weighing 3.3 mg of molybdenum disulfide (A-1) obtained in Synthesis Example 2 into a glass vial, 10 g of NISSAN Strong Save X 0W-8 was added as a liquid medium, and then ultrasonication was applied for 1 hour. A comparative dispersion was obtained. When the obtained comparative dispersion was allowed to stand at room temperature for 1000 hours and sedimentation was confirmed, the sedimentation score was 1.
  • Comparative examples 2, 3 to 10 The sedimentation property of Daizo's M5 powder (hereinafter referred to as commercially available molybdenum disulfide) was confirmed using the dispersant (B-1) oleylamine in the same manner as in Example 1, and the sedimentation property score was 1. Comparative Examples 3 to 10 were examined in the same manner.
  • the particle size distribution of commercially available molybdenum disulfide was measured using a dynamic light scattering particle size distribution analyzer, and the median diameter D50 was determined to be 600 nm.
  • the thickness of this commercially available molybdenum disulfide was measured using AFM, the thickness was 400 nm. Therefore, the value of the aspect ratio (length (vertical)/thickness (height)) was 1.5.
  • Example 21 Comparative Example 11 Using the dispersion 1 of Example 1 and the liquid medium NISSAN Strong Save I did it.
  • the values were measured after sliding at each temperature for 7 minutes and 30 seconds. The results are shown in Table 4. In the range from 40°C to 80°C, the dispersion of Example 1 showed a low coefficient of friction and good results.
  • Examples 22-41 In the same manner as in Example 1 except that the dispersant and liquid medium were changed, the settling properties after 1000 hours were confirmed using various dispersants.
  • Oleyl phosphate was purchased from Tokyo Chemical Industry.
  • (9Z)-9-Octadecene-1-thiol was purchased from Sigma-Aldrich.
  • (9E)-9-1-(Butylthio)-9-octadecene and Di-(2E)-2-buten-1-yl disulfide were purchased from Aurora building. The results are shown in Table 5.
  • Comparative examples 12, 13 to 15 When the sedimentation property of commercially available molybdenum disulfide was confirmed using various dispersants in the same manner as in Comparative Example 2, the sedimentation property score was 1. Comparative Examples 12 to 14 were examined in the same manner. The results are shown in Table 6.
  • Example 42 Comparative Examples 16 to 18 Multemp PS manufactured by Kyodo Yushi Co., Ltd. was added as a liquid medium to 3 g of the molybdenum disulfide paste obtained in Example 1, and after preliminary kneading by hand, the disulfide was stirred for 1 minute at 2000 rpm with an autorotation mixer. A dispersion 42 of molybdenum was obtained. An SRV test was conducted on the obtained dispersion 42. The measurement conditions were a surface pressure of 200 N, an amplitude of 1 mm, a test temperature of 80° C., a frequency of 50 Hz, and a test time of 120 minutes. Table 7 shows the measurement results of the dynamic friction coefficient of the sample and after 60 minutes.
  • Example 42 The smaller the friction coefficient, the more the friction can be reduced, indicating that molybdenum disulfide, which contributes to friction improvement, can be efficiently dispersed.
  • the dispersion of Example 42 showed good results with a low coefficient of friction.
  • Example 1 Application Evaluation Using the dispersions of Example 1, Comparative Example 1 (no dispersant used), and Comparative Example 6 (M5 powder only), evaluation was performed on engine filter permeability.
  • the filters used were an oil element filter (manufactured by UNION SANGYO, O-103), and disc filters 25CS020AN (200 nm) and 25CS080AN (800 nm) (manufactured by Toyo Roshi Co., Ltd.).
  • Evaluation criteria 5 There is no change in the color of the oil before and after passing through the filter, and there is almost no change in viscosity. 4: There is a slight change in the color of the oil before and after passing through the filter. 3: There is a change in the color of the oil before and after passing through the filter. 2: The oil is nearly transparent after passing through the filter. 1: When passing through the filter, clear trapped matter was observed on the filter, and the oil after passing was also nearly transparent.

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JP2019502810A (ja) * 2016-01-05 2019-01-31 ナノテック・インダストリアル・ソリューションズ、インクＮａｎｏｔｅｃｈ Ｉｎｄｕｓｔｒｉａｌ Ｓｏｌｕｔｉｏｎｓ， Ｉｎｃ． 水性ナノ粒子ディスパージョン
CN106350195A (zh) * 2016-08-24 2017-01-25 合肥学院 一种实现二硫化钼纳米微粒在润滑油中达到溶液级分散的方法
CN108929742A (zh) * 2018-08-31 2018-12-04 清华大学 纳米二硫化钼润滑油及其制备方法
WO2021117666A1 (ja) * 2019-12-09 2021-06-17 Dic株式会社 潤滑剤及び潤滑組成物

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