WO2016043334A1 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- WO2016043334A1 WO2016043334A1 PCT/JP2015/076809 JP2015076809W WO2016043334A1 WO 2016043334 A1 WO2016043334 A1 WO 2016043334A1 JP 2015076809 W JP2015076809 W JP 2015076809W WO 2016043334 A1 WO2016043334 A1 WO 2016043334A1
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- lubricating oil
- oil composition
- viscosity
- comb polymer
- group
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- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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- C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
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- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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Definitions
- the present invention relates to a lubricating oil composition.
- Patent Document 1 includes a lubricant base oil, an ashless dispersant, a polymethacrylate-based viscosity index improver having a PSSI (permanent shear stability index) in a predetermined range, and the like at a viscosity index of 100 ° C.
- PSSI permanent shear stability index
- Patent Document 1 states that the lubricating oil composition for an internal combustion engine has a higher torque reduction rate under a condition where the oil temperature is 80 ° C. and better fuel efficiency in a high temperature region than the conventional lubricating oil composition. It is shown.
- the fuel efficiency of engine oil has been generally targeted at the fuel efficiency in the temperature range of about 80 to 100 ° C. mainly after the engine warm-up operation is completed.
- fuel efficiency is also required in a low temperature range of about 25 to 60 ° C. when the engine is started.
- Patent Document 1 although there is a study on fuel efficiency at 80 ° C. assuming the end of the warm-up operation of the engine, there is no study on fuel efficiency in a low temperature region assuming engine startup. Further, as a result of studies by the present inventors, it has been found that the lubricating oil composition for an internal combustion engine described in Patent Document 1 has a problem that fuel efficiency is inferior in a low temperature region assumed when the engine is started.
- the present invention provides a lubricating oil composition that is excellent in fuel-saving performance under a low temperature range assuming engine starting while improving various properties such as viscosity under a high temperature range assuming high speed operation of the engine.
- the purpose is to provide.
- the present inventors include a viscosity index improver containing a comb polymer together with a base oil and having an SSI (shear stability index) adjusted to a predetermined range, and have a predetermined HTHS viscosity at 150 ° C. and a kinematic viscosity at 40 ° C.
- SSI sinosity index
- the present inventors have found that a lubricating oil composition adjusted to the above range can solve the above problems, and completed the present invention.
- a lubricating oil composition having a ratio (V 40 / T 150 ) of 12.4 or less to a viscosity (T 150 ) [mPa ⁇ s].
- a method of using a lubricating oil composition wherein the lubricating oil composition according to [1] is used in a low temperature range of 10 to 60 ° C.
- a viscosity index improver (A) containing a comb polymer and having an SSI (shear stability index) of 30 or less is added to the base oil, HTHS viscosity at 150 ° C. (high temperature high shear viscosity) (T 150 ) is 1.6 to 2.9 mPa ⁇ s, kinematic viscosity at 40 ° C. (V 40 ) [mm 2 / s], and HTHS at 150 ° C.
- a method for producing a lubricating oil composition comprising the step (I) of preparing a lubricating oil composition having a ratio (V 40 / T 150 ) to a viscosity (T 150 ) [mPa ⁇ s] of 12.4 or less. .
- the lubricating oil composition of the present invention is excellent in fuel saving performance under a low temperature range assuming engine starting while improving various properties such as viscosity under a high temperature range assuming high speed operation of the engine.
- kinematic viscosity at 40 ° C. or 100 ° C.” and “viscosity index” mean values measured in accordance with JIS K 2283.
- HTHS viscosity at 150 ° C. or 100 ° C.” is a value of high-temperature high viscosity at 150 ° C. or 100 ° C. measured according to ASTM D 4741, specifically The value obtained by the measuring method described in the examples is meant.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically described in the examples. Means the value measured with the measurement device and measurement conditions.
- under a high temperature region assuming high speed operation of the engine refers to an environment in a temperature range of usually 80 to 180 ° C. (preferably 80 to 150 ° C.).
- under a low temperature range assuming engine start refers to an environment in a temperature range of 10 to 60 ° C. (preferably 20 to 60 ° C.).
- (meth) acrylate is used as a word indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms and similar notations.
- alkali metal atom a lithium atom (Li), a sodium atom (Na), a potassium atom (K), a rubidium atom (Rb), a cesium atom (Cs), and a francium atom (Fr) are used. Point to.
- the “alkaline earth metal atom” refers to a beryllium atom (Be), a magnesium atom (Mg), a calcium atom (Ca), a strontium atom (Sr), and a barium atom (Ba).
- the lubricating oil composition of the present invention contains a comb polymer and a viscosity index improver (A) having an SSI (shear stability index) of 30 or less, together with a base oil, and has an HTHS viscosity at 150 ° C. (high temperature and high shear).
- Viscosity) (T 150 ) is 1.6 to 2.9 mPa ⁇ s, and kinematic viscosity (V 40 ) [mm 2 / s] at 40 ° C. and HTHS viscosity (T 150 ) [mPa ⁇ s at 150 ° C. ] (V 40 / T 150 ) to 12.4 or less.
- the lubricating oil composition of the present invention is required to have an HTHS viscosity (T 150 ) at 150 ° C. of 1.6 to 2.9 mPa ⁇ s. If the HTHS viscosity (T 150 ) is less than 1.6 mPa ⁇ s, the lubricating performance tends to decrease, such being undesirable. On the other hand, when the HTHS viscosity (T 150 ) exceeds 2.9 mPa ⁇ s, the viscosity characteristics at low temperature tend to be lowered and the fuel saving performance is lowered, which is not preferable.
- the HTHS viscosity (T 150 ) of the lubricating oil composition at 150 ° C. is preferably 1.7 to 2.8 mPa ⁇ s, more preferably 1.8 to 2.2. It is 8 mPa ⁇ s, more preferably 1.9 to 2.7 mPa ⁇ s, and still more preferably 2.0 to 2.7 mPa ⁇ s.
- the HTHS viscosity (T 0.99) can also be envisaged as a viscosity under a high temperature region at the time of high-speed operation of the engine. That is, if the HTHS viscosity (T 150 ) at 150 ° C. of the obtained lubricating oil composition falls within the above range, the lubricating oil composition has a viscosity under a high temperature region assuming high-speed operation of the engine. It can be said that the various properties of are good.
- the lubricating oil composition of the present invention requires that the ratio (V 40 / T 150 ) between the kinematic viscosity (V 40 ) at 40 ° C. and the HTHS viscosity (T 150 ) at 150 ° C. is 12.4 or less. .
- the present inventors have found that the ratio (V 40 / T 150 ) serves as an index of fuel saving performance under a low temperature region assumed at the time of engine start, and completed the present invention. That is, the lubricating oil composition having the ratio (V 40 / T 150 ) exceeding 12.4 has insufficient fuel saving performance in a low temperature region assumed when the engine is started.
- the ratio (V 40 / T 150 ) between the kinematic viscosity (V 40 ) at 40 ° C. and the HTHS viscosity (T 150 ) at 150 ° C. of the lubricating oil composition of one embodiment of the present invention is preferably 12 .2 or less, more preferably 12.0 or less, still more preferably 11.7 or less, and still more preferably 11.5 or less.
- the lower limit of the ratio (V 40 / T 150 ) is not particularly limited, but the ratio (V 40 / T 150 ) is usually 6.00 or more, Preferably it is 8.00 or more.
- the HTHS viscosity (T 150 ) and the ratio (V 40 / T 150 ) are mainly determined by the degree of purification, content, kinematic viscosity, and viscosity index of the base oil used. And comb polymer content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), viscosity index improver (A) SSI, viscosity index improver (A) content, etc. It is possible to adjust by doing.
- a comb polymer as a viscosity index improver, it contributes to the adjustment of the HTHS viscosity (T 150 ) and the ratio (V 40 / T 150 ).
- T 150 the HTHS viscosity
- V 40 the ratio of the HTHS viscosity
- V 40 the kinematic viscosity under the low temperature region of the resulting lubricating oil composition
- the comb polymer has the property of maintaining a certain viscosity or higher without being reduced in viscosity even under shearing under a high temperature region. Therefore, by increasing the content ratio of the comb polymer in the viscosity index improver (A), the value of the HTHS viscosity (T 150 ) is adjusted to be high even if the total amount of the viscosity index improver (A) is relatively small. Easy to do.
- a comb polymer having a lower molecular weight distribution (Mw / Mn) is more likely to exhibit the above properties under a low temperature region and a high temperature region, and the HTHS viscosity (T 150 ) and the ratio (V 40 / T 150 ) are described above. There is a tendency to be easily adjusted in the range.
- the values of the HTHS viscosity (T 150 ) and the ratio (V 40 / T 150 ) can be adjusted by considering the above items (a) to (e) in appropriate combination.
- the above items (a) to (e) are merely examples, and are not limited to these items.
- the results of this embodiment described later may be appropriately taken into account. It can be adjusted.
- the HTHS viscosity (T 100 ) at 100 ° C. of the lubricating oil composition of one embodiment of the present invention is preferably 3.0 to 6.0 mPa ⁇ s from the viewpoint of improving lubricating performance, viscosity characteristics, and fuel economy. More preferably, it is 3.5 to 5.8 mPa ⁇ s, still more preferably 4.0 to 5.6 mPa ⁇ s, and still more preferably 4.2 to 5.3 mPa ⁇ s.
- the ratio (T 150 / T 100 ) of the HTHS viscosity at 150 ° C. (T 150 ) and the HTHS viscosity at 100 ° C. (T 100 ) of the lubricating oil composition of one embodiment of the present invention is as follows: From the viewpoint of improving fuel economy, it is preferably 0.50 or more, more preferably 0.51 or more, still more preferably 0.53 or more, and still more preferably 0.54 or more.
- the kinematic viscosity (V 40 ) at 40 ° C. of the lubricating oil composition of one embodiment of the present invention is preferably 10.0 to 40.0 mm 2 / from the viewpoint of improving lubricating performance, viscosity characteristics, and fuel economy. s, more preferably 15.0 ⁇ 38.0 mm 2 / s, more preferably 20.0 ⁇ 35.0 mm 2 / s, still more preferably 22.0 ⁇ 32.0 mm 2 / s, even more preferably 24 0.0 to 29.9 mm 2 / s.
- the kinematic viscosity (V 100 ) at 100 ° C. of the lubricating oil composition of one embodiment of the present invention is preferably 4.0 to 12.5 mm 2 / from the viewpoint of improving lubricating performance, viscosity characteristics, and fuel economy. s, more preferably 5.0 ⁇ 11.0 mm 2 / s, more preferably 5.5 ⁇ 10.0 mm 2 / s, even more preferably 6.0 ⁇ 9.3mm 2 / s.
- the viscosity index of the lubricating oil composition of one embodiment of the present invention is preferably 140 or more, more preferably 155 or more, still more preferably 170 or more, from the viewpoint of suppressing the change in viscosity due to temperature change and improving fuel economy. More preferably, it is 190 or more.
- the lubricating oil composition of one aspect of the present invention contains a viscosity index improver (A) containing a comb polymer together with a base oil, but is used in a more general lubricating oil as long as the effects of the present invention are not impaired.
- the lubricating oil additive may be contained.
- the total content of the base oil and the viscosity index improver (A) is preferably 70% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. More preferably 75% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, still more preferably 90% by mass or more, and usually 100% by mass or less, more preferably 99.9% by mass. % Or less, more preferably 99% by mass or less.
- each component contained in the lubricating oil composition of one embodiment of the present invention will be described.
- the base oil contained in the lubricating oil composition of one embodiment of the present invention may be mineral oil, synthetic oil, or a mixed oil of mineral oil and synthetic oil.
- Mineral oil includes, for example, atmospheric residue obtained by atmospheric distillation of paraffinic, intermediate, naphthenic, etc. crude oil; distillate obtained by vacuum distillation of the atmospheric residue; Mineral oils and waxes that have been subjected to one or more purification processes such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc .; by Fischer-Tropsch method, etc. Examples thereof include mineral oils obtained by isomerizing the produced wax (GTL wax (Gas To Liquids WAX)).
- mineral oils and waxes that have been subjected to one or more purification processes such as solvent deburring, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, and the like are preferable.
- API American Petroleum Institute
- Mineral oils classified into Group 2 and Group 3 of the base oil category are more preferred, and mineral oils classified into Group 3 are more preferred.
- Synthetic oils include, for example, polybutene and ⁇ -olefin homopolymers or copolymers (eg, ⁇ -olefin homopolymers or copolymers having 8 to 14 carbon atoms such as ethylene- ⁇ -olefin copolymers).
- Poly ⁇ -olefins such as polyol esters, various esters such as dibasic acid esters and phosphate esters; various ethers such as polyphenyl ethers; polyglycols; alkyl benzenes; alkyl naphthalenes; waxes produced by the Fischer-Tropsch method ( Synthetic oils obtained by isomerizing (GTL wax). Of these synthetic oils, poly ⁇ -olefins are preferred.
- the base oil used in one embodiment of the present invention is selected from mineral oils classified into Group 2 and Group 3 of the API (American Petroleum Institute) base oil category and synthetic oils from the viewpoint of oxidation stability of the base oil itself. 1 or more types are preferable, and 1 or more types selected from the mineral oil classified into the group 3 and the poly ⁇ -olefin are more preferable. In one embodiment of the present invention, these base oils may be used alone or in combination of two or more.
- the kinematic viscosity at 100 ° C. of the base oil used in one embodiment of the present invention is preferably 2.0 to 20.0 mm 2 / s, more preferably 2.0 to 15.0 mm 2 / s, and still more preferably 2.
- the thickness is 0 to 10.0 mm 2 / s, more preferably 2.0 to 7.0 mm 2 / s. If the kinematic viscosity at 100 ° C. of the base oil is 2.0 mm 2 / s or more, it is preferable because the evaporation loss is small. On the other hand, if the kinematic viscosity at 100 ° C. of the base oil is 20.0 mm 2 / s or less, it is preferable because power loss due to viscous resistance can be suppressed and a fuel efficiency improvement effect can be obtained.
- the viscosity index of the base oil used in one embodiment of the present invention is preferably 80 or more, more preferably 90 or more, and still more preferably 100 from the viewpoint of suppressing the change in viscosity due to a temperature change and improving fuel economy. That's it.
- the kinematic viscosity and viscosity index of the said mixed oil are the said range.
- the base oil content is preferably 55% by mass or more, more preferably 60% by mass or more, based on the total amount (100% by mass) of the lubricating oil composition.
- it is 65 mass% or more, More preferably, it is 70 mass% or more, Preferably it is 99 mass% or less, More preferably, it is 95 mass% or less.
- the lubricating oil composition of the present invention comprises a viscosity index improver (A) containing a comb polymer and having an SSI of 30 or less.
- a viscosity index improver (A) containing a comb polymer and having an SSI of 30 or less.
- the viscosity index improver (A) used in one embodiment of the present invention is an unreacted raw material compound used in synthesizing other resin components or comb polymers not corresponding to the comb polymer, as long as the effects of the present invention are not impaired. Further, by-products such as a resin component that does not correspond to the catalyst and the comb polymer generated at the time of synthesis may be contained.
- the above-mentioned “resin content” means a polymer having a weight average molecular weight (Mw) of 1000 or more and having a certain repeating unit.
- resin components not applicable to comb polymers include, for example, polymethacrylates, dispersed polymethacrylates, olefin copolymers (for example, ethylene-propylene copolymers), dispersed olefin copolymers, styrene series Polymers that do not fall under comb polymers such as copolymers (for example, styrene-diene copolymers, styrene-isoprene copolymers, etc.) can be mentioned.
- these other resin components may be contained not as the viscosity index improver (A) but as a general-purpose additive such as a pour point depressant if it is a polymethacrylate compound, for example.
- a comb polymer in the lubricating oil composition of one embodiment of the present invention, from the viewpoint of adjusting the SSI value of the viscosity index improver, and from the viewpoint of improving the fuel saving performance under a low temperature region assumed at the time of engine start, a comb polymer
- the content of other resin components that do not fall under (especially polymethacrylate compounds) is preferably as small as possible.
- the content of the polymethacrylate compound not corresponding to the comb polymer is preferably 0 to 30 parts by mass, more preferably 0 to 25 parts per 100 parts by mass of the comb polymer contained in the lubricating oil composition. Part by mass, more preferably 0 to 20 parts by mass, and still more preferably 0 to 15 parts by mass.
- the content of the above-mentioned by-product is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably based on the total amount of solid content (100% by mass) in the viscosity index improver (A). Is 1% by mass or less, more preferably 0.1% by mass or less.
- said "solid content in a viscosity index improver (A)” means the component remove
- the content of the comb polymer in the viscosity index improver (A) used in one embodiment of the present invention is preferably 60 to 100, based on the total amount (100% by mass) of the solid content in the viscosity index improver (A). % By mass, more preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and still more preferably 99 to 100% by mass. .
- the viscosity index improver (A) used in one embodiment of the present invention includes a comb polymer as a resin component, but usually a resin such as a comb polymer in consideration of handling properties and solubility in the above base oil.
- the solid content including a component is commercially available in the form of a solution dissolved in a diluent oil such as mineral oil or synthetic oil.
- the viscosity index improver (A) used in one embodiment of the present invention is in the form of the above solution, the solid content concentration of the solution is usually 10 to 50 mass based on the total amount (100 mass%) of the solution. %.
- the content of the viscosity index improver (A) improves the viscosity characteristics, and from the viewpoint of improving the fuel saving performance under both the high temperature region and the low temperature region.
- the total amount (100% by mass) of the lubricating oil composition is preferably 0.01 to 10.00% by mass, more preferably 0.05 to 8.00% by mass, and more preferably 0.10 to 6. It is 50% by mass, more preferably 0.50 to 5.00% by mass, and still more preferably 0.90 to 4.00% by mass.
- the “content of the viscosity index improver (A)” is a solid content including a comb polymer and the above-mentioned other resin, and does not include the mass of the diluent oil.
- SSI means the shear stability index (Shear Stability Index), and indicates the decrease in viscosity due to shear derived from the resin component in the viscosity index improver as a percentage.
- the SSI of the viscosity index improver (A) is a value measured according to ASTM D6278, and specifically, a value calculated from the following calculation formula (1).
- Kv 0 is the value of the kinematic viscosity at 100 ° C. of the viscosity index improver containing the resin component
- Kv 1 is 30 cycles of the viscosity index improver according to the procedure of ASTM D6278. It is the value of kinematic viscosity at 100 ° C. after passing through a high shear Bosch diesel injector.
- Kv oil is a kinematic viscosity value at 100 ° C. of the composition of the viscosity index improver and the diluent oil.
- the SSI of the viscosity index improver (A) used in the present invention is 30 or less, preferably 25 or less, more preferably 20 from the viewpoint of improving the fuel saving performance under a low temperature region assuming engine starting. Hereinafter, it is more preferably 15 or less, and still more preferably 10 or less. If the SSI of the viscosity index improver (A) exceeds 30, fuel economy performance tends to be insufficient under a low temperature range assuming engine startup. Moreover, about the lubricating oil composition obtained, a viscosity fall at high temperature is caused with time, and it becomes easy to produce wear and damage of components.
- SSI of a viscosity index improver (A) is 1 or more normally, Preferably it is 2 or more.
- the SSI value of the viscosity index improver (A) varies depending on the resin content structure of the viscosity index improver (A). Specifically, there is a tendency shown below, and the SSI value of the viscosity index improver (A) can be easily adjusted by considering these matters. However, the following items are merely examples, and are not limited to these items. For example, the adjustment can be made by appropriately taking into account the results of the present embodiment described later.
- the value of SSI such as PMA used as a viscosity index improver tends to increase.
- the SSI of the viscosity index improver tends to decrease.
- the comb polymer used in the present invention tends to have a low SSI value due to its comb structure. Therefore, the SSI value of the viscosity index improver (A) tends to be lowered by increasing the content ratio of the comb polymer in the viscosity index improver (A). -The SSI value tends to decrease as the content ratio of the comb polymer having a large content of the structural unit (I) derived from the macromonomer (I ') corresponding to the side chain of the comb polymer increases. -As the content of the comb polymer having a high molecular weight side chain increases, the SSI value tends to decrease.
- the “comb polymer” contained in the viscosity index improver (A) used in the present invention refers to a polymer having a structure having a number of trident branching points with a high molecular weight side chain in the main chain.
- a polymer having at least the structural unit (I) derived from the macromonomer (I ′) is preferable.
- This structural unit (I) corresponds to the above “high molecular weight side chain”.
- the above “macromonomer” means a high molecular weight monomer having a polymerizable functional group, and is preferably a high molecular weight monomer having a polymerizable functional group at the terminal.
- Comb polymers have a structure in which the distance between the trifurcated branch points of the main chain is long and the main chain with high polarity can easily come into contact with the base oil, but this main chain dissolves in the base oil in the low temperature region. It is hard to do. Therefore, the comb polymer exhibits a property that it is difficult to increase the viscosity under a low temperature region, and the lubricating oil composition containing the comb polymer has a low kinematic viscosity (V 40 ) that is a kinematic viscosity under the low temperature region. It is easy to become.
- V 40 low kinematic viscosity
- the comb-shaped polymer has a property that the main chain easily spreads in the base oil under a high temperature region, and the property of being easily thickened is expressed, and the viscosity of a certain level or more can be maintained. Therefore, the value of the HTHS viscosity (T 150 ) of the lubricating oil composition containing the comb polymer tends to be high.
- the number average molecular weight (Mn) of the macromonomer (I ′) is preferably 200 or more, more preferably 500 or more, still more preferably 600 or more, still more preferably 700 or more, and preferably 200,000 or less. More preferably, it is 100,000 or less, More preferably, it is 50,000 or less, More preferably, it is 20,000 or less.
- Examples of the polymerizable functional group possessed by the macromonomer (I ′) include an acryloyl group (CH 2 ⁇ CH—COO—), a methacryloyl group (CH 2 ⁇ CCH 3 —COO—), and an ethenyl group (CH 2 ⁇ CH—). ), Vinyl ether group (CH 2 ⁇ CH—O—), allyl group (CH 2 ⁇ CH—CH 2 —), allyl ether group (CH 2 ⁇ CH—CH 2 —O—), CH 2 ⁇ CH—CONH— And a group represented by CH 2 ⁇ CCH 3 —CONH—.
- the macromonomer (I ′) may have, for example, one or more repeating units represented by the following general formulas (i) to (iii).
- R 1 represents a linear or branched alkylene group having 1 to 10 carbon atoms, specifically, methylene group, ethylene group, 1,2-propylene group, 1,3- Propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, isopropyl group, isobutyl group, 2- Examples thereof include an ethylhexylene group.
- R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, Examples include 1,2-butylene group, 1,3-butylene group, 1,4-butylene group and the like.
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a linear or branched alkyl group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl.
- R 1 , R 2 , R 3 and R 4 may be the same or different from each other. It may be.
- the form of copolymerization is a block copolymer. It may be a random copolymer.
- the comb polymer used in one embodiment of the present invention may be a homopolymer composed only of the structural unit (I) derived from one type of macromonomer (I ′) or may be derived from two or more types of macromonomer (I ′).
- a copolymer containing the structural unit (I) may be used.
- the comb polymer used in one embodiment of the present invention includes a structural unit derived from a monomer (II ′) other than the macromonomer (I ′) together with the structural unit (I) derived from the macromonomer (I ′). It may be a copolymer containing II).
- the specific structure of such a comb polymer includes the structural unit (I) derived from the macromonomer (I ′) with respect to the main chain including the structural unit (II) derived from the monomer (II ′).
- a copolymer having a side chain is preferred.
- the distance between the trident branch points of the main chain having a high molecular weight side chain derived from the macromonomer (I ′) increases. .
- the value of the kinematic viscosity (V 40 ) can be easily adjusted to be low, and since the viscosity becomes high under the high temperature region, the value of the HTHS viscosity (T 150 ) is easily adjusted to be high. .
- Examples of the monomer (II ′) include a monomer (a) represented by the following general formula (a1), an alkyl (meth) acrylate (b), a nitrogen atom-containing vinyl monomer (c), and a hydroxyl group-containing vinyl.
- the monomer (II ′) is preferably a monomer other than the aromatic hydrocarbon vinyl monomer (h).
- R 11 represents a hydrogen atom or a methyl group.
- R 12 represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, —O— or —NH—.
- R 13 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
- N represents an integer of 1 or more (preferably an integer of 1 to 20, more preferably an integer of 1 to 5).
- n is an integer of 2 or more, the plurality of R 13 may be the same or different, and the (R 13 O) n portion may be a random bond or a block bond.
- R 14 represents a linear or branched alkyl group having 1 to 60 carbon atoms (preferably 10 to 50, more preferably 20 to 40).
- linear or branched alkylene group having 1 to 10 carbon atoms “linear or branched alkylene group having 2 to 4 carbon atoms”, and “linear or branched alkyl group having 1 to 60 carbon atoms”
- Specific examples of the group include the same groups as those exemplified in the description relating to the general formulas (i) to (iii).
- alkyl (meth) acrylate (b) examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-t-butylheptyl (meth) acrylate, octyl (meth) acrylate, Examples include 3-isopropylheptyl (meth) acrylate.
- the carbon number of the alkyl group contained in the alkyl (meth) acrylate (b) is preferably 1 to 30, more preferably 1
- nitrogen atom-containing vinyl monomer (c) examples include an amide group-containing vinyl monomer (c1), a nitro group-containing monomer (c2), and a primary amino group-containing vinyl monomer (c3), 2 Examples thereof include a tertiary amino group-containing vinyl monomer (c4), a tertiary amino group-containing vinyl monomer (c5), and a nitrile group-containing vinyl monomer (c6).
- Examples of the amide group-containing vinyl monomer (c1) include (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn- or isobutyl.
- Monoalkylamino (meth) acrylamides such as (meth) acrylamide; N-methylaminoethyl (meth) acrylamide, N-ethylaminoethyl (meth) acrylamide, N-isopropylamino-n-butyl (meth) acrylamide and Nn -Or monoalkylaminoalkyl (meth) acrylamides such as isobutylamino-n-butyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meta) Acrylic net And dialkylamino (meth) acrylamides such as N, N-di-n-butyl (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth)
- nitro group-containing monomer (c2) examples include 4-nitrostyrene.
- Examples of the primary amino group-containing vinyl monomer (c3) include alkenylamines having an alkenyl group having 3 to 6 carbon atoms such as (meth) allylamine and crotylamine; and 2 to 2 carbon atoms such as aminoethyl (meth) acrylate. Aminoalkyl (meth) acrylate having 6 alkyl groups; and the like.
- Examples of the secondary amino group-containing vinyl monomer (c4) include monoalkylaminoalkyl (meth) acrylates such as t-butylaminoethyl (meth) acrylate and methylaminoethyl (meth) acrylate; di (meth) allylamine And the like, and the like.
- Examples of the tertiary amino group-containing vinyl monomer (c5) include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; nitrogen such as morpholinoethyl (meth) acrylate Atom-containing alicyclic (meth) acrylate; diphenylamine (meth) acrylamide, N, N-dimethylaminostyrene, 4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone and N-vinylthiopyrrolidone And their hydrochlorides, sulfates, phosphates or lower alkyl (C 1-8) monocarboxylic acids (such as acetic acid and propionic acid) salts; and the like.
- dialkylaminoalkyl (meth) acrylates such as dimethylaminoe
- Examples of the nitrile group-containing vinyl monomer (c6) include (meth) acrylonitrile.
- hydroxyl group-containing vinyl monomer (d) examples include a hydroxyl group-containing vinyl monomer (d1) and a polyoxyalkylene chain-containing vinyl monomer (d2).
- hydroxyl group-containing vinyl monomer (d1) examples include hydroxyl group-containing aromatic vinyl monomers such as p-hydroxystyrene; 2-hydroxyethyl (meth) acrylate, and 2- or 3-hydroxypropyl (meta) ) Hydroxyalkyl (meth) acrylate having an alkyl group of 2 to 6 carbon atoms such as acrylate; N, N-dihydroxymethyl (meth) acrylamide, N, N-dihydroxypropyl (meth) acrylamide, N, N-di-2 Mono- or di-hydroxyalkyl substituted (meth) acrylamides having 1 to 4 carbon atoms such as hydroxybutyl (meth) acrylamide; vinyl alcohol; (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol and 1-undece Alkenols having 3 to 12 carbon atoms such as alcohol; alkene monools or alkenes having 4 to 12 carbon atoms
- polyoxyalkylene chain-containing vinyl monomer (d2) examples include polyoxyalkylene glycol (alkylene group having 2 to 4 carbon atoms, polymerization degree of 2 to 50), polyoxyalkylene polyol (polyhydric alcohol polysiloxane described above).
- Oxyalkylene ether (alkylene group having 2 to 4 carbon atoms, degree of polymerization 2 to 100)), polyoxyalkylene glycol or polyoxyalkylene polyol alkyl (carbon number 1 to 4) ether mono (meth) acrylate [polyethylene glycol ( Mn: 100 to 300) mono (meth) acrylate, polypropylene glycol (Mn: 130 to 500) mono (meth) acrylate, methoxypolyethylene glycol (Mn: 110 to 310) (meth) acrylate, lauryl alcohol ethylene oxide addition (2-30 moles) (meth) acrylate and mono (meth) acrylic acid polyoxyethylene (Mn: 0.99 ⁇ 230) sorbitan etc.] and the like.
- Phosphorus atom-containing monomer (e) examples include a phosphate ester group-containing monomer (e1) and a phosphono group-containing monomer (e2).
- Examples of the phosphate ester group-containing monomer (e1) include (meth) acryloyl having an alkyl group having 2 to 4 carbon atoms such as (meth) acryloyloxyethyl phosphate and (meth) acryloyloxyisopropyl phosphate.
- Roxyalkyl phosphate ester C2-C12 such as vinyl phosphate, allyl phosphate, propenyl phosphate, isopropenyl phosphate, butenyl phosphate, pentenyl phosphate, octenyl phosphate, decenyl phosphate and dodecenyl phosphate Alkenyl phosphate having an alkenyl group; and the like.
- Examples of the phosphono group-containing monomer (e2) include (meth) acryloyloxyalkylphosphonic acids having 2 to 4 carbon atoms such as (meth) acryloyloxyethylphosphonic acid; vinylphosphonic acid, allyl And alkenylphosphonic acids having an alkenyl group having 2 to 12 carbon atoms such as phosphonic acid and octenylphosphonic acid.
- aliphatic hydrocarbon vinyl monomer (f) examples include ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene and other alkenes having 2 to 20 carbon atoms; butadiene, isoprene , 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene and the like, such as alkadienes having 4 to 12 carbon atoms;
- the carbon number of the aliphatic hydrocarbon vinyl monomer (f) is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 12.
- alpha-1 hydrocarbon vinyl monomer (g) examples include cyclohexene, (di) cyclopentadiene, pinene, limonene, vinylcyclohexene, and ethylidenebicycloheptene.
- the carbon number of the alicyclic hydrocarbon-based vinyl monomer (g) is preferably 3 to 30, more preferably 3 to 20, and still more preferably 3 to 12.
- aromatic hydrocarbon vinyl monomer (h) examples include styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4 -Butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, p-methylstyrene, monochlorostyrene, dichlorostyrene, tribromostyrene, tetrabromostyrene, 4-crotylbenzene, indene and 2-vinylnaphthalene Etc.
- the carbon number of the aromatic hydrocarbon vinyl monomer (h) is preferably 8 to 30, more preferably 8 to 20, and still more preferably 8 to 18.
- vinyl esters (i) examples include vinyl esters of saturated fatty acids having 2 to 12 carbon atoms such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl octoate.
- vinyl ethers (j) examples include alkyl vinyl ethers having 1 to 12 carbon atoms such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and 2-ethylhexyl vinyl ether; aryl vinyl ethers having 6 to 12 carbon atoms such as phenyl vinyl ether.
- An alkoxyalkyl vinyl ether having 1 to 12 carbon atoms such as vinyl-2-methoxyethyl ether and vinyl-2-butoxyethyl ether.
- vinyl ketones (k) examples include alkyl vinyl ketones having 1 to 8 carbon atoms such as methyl vinyl ketone and ethyl vinyl ketone; aryl vinyl ketones having 6 to 12 carbon atoms such as phenyl vinyl ketone.
- Epoxy group-containing vinyl monomer (l) examples include glycidyl (meth) acrylate and glycidyl (meth) allyl ether.
- Halogen-containing vinyl monomer (m) examples include vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, halogenated styrene (dichlorostyrene and the like), and the like.
- Unsaturated polycarboxylic acid ester (n) examples include an unsaturated polycarboxylic acid alkyl ester, an unsaturated polycarboxylic acid cycloalkyl ester, and an unsaturated polycarboxylic acid aralkyl ester.
- the acid examples include maleic acid, fumaric acid, itaconic acid and the like.
- (di) alkyl fumarate (o) examples include monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, methyl ethyl fumarate, monobutyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl. Examples include fumarate.
- ((Di) alkyl maleate (p)) examples include monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, methyl ethyl maleate, monobutyl maleate, dibutyl maleate and the like.
- the weight average molecular weight (Mw) of the comb polymer used in one embodiment of the present invention is preferably 10,000 to 1,000,000, more preferably from the viewpoint of good fuel economy performance under a low temperature range assuming engine starting. Is from 30,000 to 700,000, more preferably from 60,000 to 600,000, and even more preferably from 100,000 to 550,000.
- the molecular weight distribution (Mw / Mn) of the comb polymer used in one embodiment of the present invention is preferably 6.00 or less, more preferably from the viewpoint of good fuel economy performance in a low temperature region assuming engine starting. Is 4.00 or less, more preferably 3.00 or less, even more preferably 2.00 or less, and particularly preferably less than 2.00.
- the smaller the molecular weight distribution of the comb polymer the easier it is for the properties of the above-mentioned comb polymer to be expressed under the low temperature region and the high temperature region, and the HTHS viscosity (T 150 ) and the ratio (V 40 / T 150 ) are as described above. Easy to adjust to range.
- the lubricating oil composition containing the comb polymer having a small molecular weight distribution can further improve the fuel saving performance under a low temperature region assumed when the engine is started.
- the lower limit of the molecular weight distribution of the comb polymer is not particularly limited, but the molecular weight distribution (Mw / Mn) of the comb polymer is usually 1.01 or more, preferably 1.05 or more, more preferably 1.10. That's it.
- the content of the comb polymer is adjusted so that the HTHS viscosity (T 150 ) and the ratio (V 40 / T 150 ) are adjusted to the above ranges, and the temperature is low at the time of engine start. From the viewpoint of improving the fuel saving performance under the region, it is preferably 0.01 to 10.00% by mass, more preferably 0.05 to 8%, based on the total amount (100% by mass) of the lubricating oil composition. It is 00% by mass, more preferably 0.10 to 6.50% by mass, still more preferably 0.50 to 5.00% by mass, and still more preferably 0.90 to 4.00% by mass.
- the “comb polymer content” does not include the mass of diluent oil or the like that may be contained together with the comb polymer.
- the lubricating oil composition of one embodiment of the present invention may further contain additives for lubricating oil other than the viscosity index improver, if necessary, as long as the effects of the present invention are not impaired.
- the lubricant additive include metal detergents, dispersants, antiwear agents, extreme pressure agents, antioxidants, pour point depressants, antifoaming agents, friction modifiers, rust inhibitors, metal Examples include activators. Among these, it may contain at least one additive for lubricating oil selected from metal detergents, dispersants, antiwear agents, extreme pressure agents, antioxidants, pour point depressants, and antifoaming agents. preferable.
- a commercially available additive package that is a mixture containing a plurality of additives that conforms to the API / ILSAC standard, SN / GF-5 standard, or the like may be used.
- the respective contents of these additives for lubricating oil can be adjusted as appropriate within the range not impairing the effects of the present invention, but are usually 0. 0 based on the total amount (100% by mass) of the lubricating oil composition.
- the content is 001 to 15% by mass, preferably 0.005 to 10% by mass, more preferably 0.01 to 5% by mass.
- the total content of these lubricating oil additives is preferably 30% by mass or less, based on the total amount (100% by mass) of the lubricating oil composition.
- it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.
- Metal-based detergent examples include an organometallic compound containing a metal atom selected from alkali metal atoms and alkaline earth metal atoms, specifically, metal salicylates, metal phenates, metal sulfonates, and the like. Can be mentioned.
- the metal atom contained in the metal-based detergent is preferably a sodium atom, a calcium atom, a magnesium atom, or a barium atom, more preferably a calcium atom, from the viewpoint of improving the cleanability at high temperatures.
- metal salicylate a compound represented by the following general formula (1) is preferable.
- metal phenate a compound represented by the following general formula (2) is preferable.
- metal sulfonate the following general formula (3 ) Is preferred.
- M is a metal atom selected from an alkali metal atom and an alkaline earth metal atom, and includes a sodium atom (Na), a calcium atom (Ca), a magnesium atom (Mg), Or a barium atom (Ba) is preferable and a calcium atom (Ca) is more preferable.
- p is the valence of M and is 1 or 2.
- q is an integer of 0 or more, preferably an integer of 0 to 3.
- R is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
- hydrocarbon group that can be selected as R examples include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 1 to 18 carbon atoms, cycloalkyl groups having 3 to 18 ring carbon atoms, and 6 to 18 ring carbon atoms.
- the metal detergent used in one embodiment of the present invention may be used alone or in combination of two or more. Among these, it is preferable that it is 1 or more types chosen from a calcium salicylate, a calcium phenate, and a calcium sulfonate from a viewpoint of the improvement of the cleanliness at high temperature, and a soluble viewpoint to base oil.
- the metal detergent used in one embodiment of the present invention may be any of neutral salts, basic salts, overbased salts, and mixtures thereof.
- the base value of the metal detergent is preferably 10 to 600 mgKOH / g, more preferably 20 to 500 mgKOH / g. g.
- the “base number” is the same as that in JIS K2501, “Petroleum products and lubricants—neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.
- dispersant examples include succinimide, benzylamine, succinic acid ester, and boron-modified products thereof.
- succinimide for example, a succinic acid having a polyalkenyl group such as a polybutenyl group having a molecular weight of 300 to 4,000, and a monoimide of polyethylene polyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.
- a bisimide or a modified boric acid thereof a Mannich reaction product of phenol, formaldehyde and polyethylene polyamine having a polyalkenyl group.
- Antiwear agent examples of the antiwear or extreme pressure agent include zinc dialkyldithiophosphate (ZnDTP), zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters.
- ZnDTP zinc dialkyldithiophosphate
- ZnDTP zinc dialkyldithiophosphate
- zinc phosphate zinc dithiocarbamate
- molybdenum dithiocarbamate molybdenum dithiophosphate
- disulfides sulfurized olefins
- sulfurized fats and oils sulfurized esters.
- Sulfur-containing compounds such as thiocarbonates, thiocarbamates, polysulfides; phosphorous esters, phosphate esters, phosphonate esters, and phosphorus-containing compounds such as amine salts or metal salts thereof; Sulfur and phosphorus containing antiwear agents such as acid esters, thiophosphates, thiophosphonates, and their amine or metal salts.
- ZnDTP zinc dialkyldithiophosphate
- extreme pressure agents include sulfur-based extreme pressure agents such as sulfides, sulfoxides, sulfones, thiophosphinates, halogen-based extreme pressure agents such as chlorinated hydrocarbons, and organometallic extreme pressure agents. It is done.
- antioxidant any one of known antioxidants conventionally used as an antioxidant for lubricating oils can be appropriately selected and used.
- an amine-based antioxidant, a phenol-based antioxidant, and the like Antioxidants, molybdenum-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants and the like can be mentioned.
- amine antioxidants include diphenylamine and diphenylamine antioxidants such as alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms; ⁇ -naphthylamine, alkyl substituted phenyl- ⁇ -naphthylamine having 3 to 20 carbon atoms, and the like.
- Naphthylamine antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and octadecyl-3- (3,5-diphenol).
- Monophenol antioxidants such as -tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6) -Tert-butylphenol) and the like; hindered phenol antioxidants; and the like.
- Examples of the molybdenum-based antioxidant include molybdenum amine complex formed by reacting molybdenum trioxide and / or molybdic acid with an amine compound.
- Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate.
- Examples of phosphorus antioxidants include phosphites. These antioxidants may be used singly or in combination of two or more, but it is usually preferable to use two or more in combination.
- pour point depressant examples include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene and the like.
- Examples of the antifoaming agent include silicone oil, fluorosilicone oil, and fluoroalkyl ether.
- friction modifier examples include molybdenum-based friction modifiers such as molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and an amine salt of molybdate; an alkyl group or alkenyl group having 6 to 30 carbon atoms in the molecule.
- Ashless friction modifiers such as aliphatic amines, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, and aliphatic ethers, which have at least one;
- anti-rust examples include petroleum sulfonate, alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
- Metal deactivator examples include benzotriazole compounds, tolyltriazole compounds, thiadiazole compounds, imidazole compounds, pyrimidine compounds, and the like.
- the lubricating oil composition of the present invention is excellent in fuel saving performance under a low temperature region assumed at the time of starting the engine, while improving various properties such as viscosity under a high temperature region assumed at the time of high speed operation of the engine. Therefore, the engine filled with the lubricating oil composition of the present invention can be excellent in fuel saving performance not only at high speed operation but also when used in a low temperature region at the time of engine start. Although there is no restriction
- the present invention also provides a method for using the lubricating oil composition, wherein the lubricating oil composition of the present invention is used in a low temperature range of 10 to 60 ° C.
- the temperature under the low temperature region is a temperature range that is assumed when the engine is started, and is usually 10 to 60 ° C., preferably 20 to 60 ° C.
- the lubricating oil composition of one embodiment of the present invention is suitable for use as an engine oil for automobiles, but can also be applied to other uses.
- Other possible uses for the lubricating oil composition of one aspect of the present invention include, for example, power steering oil, automatic transmission oil (ATF), continuously variable transmission oil (CVTF), hydraulic fluid, turbine oil, compressor oil, Examples include machine tool lubricating oil, cutting oil, gear oil, fluid bearing oil, rolling bearing oil, and the like.
- the present invention also provides a method for producing a lubricating oil composition having the following step (I).
- blend are as above-mentioned, and the content of a suitable component and each component is also as above-mentioned. Moreover, in this process, you may mix
- the solid content concentration of the solution is usually 10 to 50% by mass.
- the amount of the solution is the lubricating oil composition
- the content is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 2 to 20% by mass with respect to the total amount of the product (100% by mass).
- the additive for lubricating oil may be blended after adding a diluent oil or the like to form a solution (dispersion). After blending each component, it is preferable to stir and disperse uniformly by a known method.
- the lubricating oil composition obtained when a part of the components is modified after the respective components are blended or the two components react with each other to form another component also belongs to the technical scope of the present invention. It is.
- Driving torque improvement rate (%) ([Measured value of torque of lubricating oil composition to be evaluated] ⁇ [Measured value of torque of lubricating oil composition of Comparative Example 1 or 4]) / [Comparative Example 1 or 4 Measured value of torque of lubricating oil composition] ⁇ 100 The larger the number, the better the driving torque and the higher fuel efficiency.
- each component of the lubricating oil composition prepared by the present Example and the comparative example is as follows.
- ⁇ Base oil> “100N mineral oil” 40 ° C. kinematic viscosity: 17.8 mm 2 / s, 100 ° C. kinematic viscosity: 4.07 mm 2 / s, viscosity index: 131, density: 0.824 g / cm 3 .
- “70N mineral oil” 40 ° C. kinematic viscosity: 12.5 mm 2 / s, 100 ° C. kinematic viscosity: 3.12 mm 2 / s, viscosity index: 110, density: 0.832 g / cm 3 .
- Viscosity index improver-A main agent containing, as the main resin component, a comb polymer (Mw: 250,000, Mw / Mn: 2.08) having at least a structural unit derived from a macromonomer having Mn of 500 or more A viscosity index improver having a resin concentration of 19% by mass and an SSI of 3.
- “Viscosity index improver-B” main agent containing a comb polymer (Mw: 420,000, Mw / Mn: 5.92) having at least a structural unit derived from a macromonomer having Mn of 500 or more as the main resin component A viscosity index improver having a resin concentration of 19% by mass and an SSI of 5.
- “Viscosity index improver-C” comb polymer (Mw: 330,000, Mw / Mn: 2.00 or more) having at least a structural unit derived from a macromonomer having Mn of 500 or more as a main resin component, A viscosity index improver having a main resin content of 25% by mass and an SSI of 5.
- “Viscosity index improver-D” comb polymer (Mw: 440,000, Mw / Mn: 2.00 or more) having at least a structural unit derived from a macromonomer having Mn of 500 or more as the main resin component A viscosity index improver having a main resin content concentration of 25% by mass and an SSI of 8.
- “Viscosity index improver-E” comb polymer (Mw: 480,000, Mw / Mn: 2.00 or more) having at least a structural unit derived from a macromonomer having Mn of 500 or more as the main resin component A viscosity index improver having a main resin content concentration of 25% by mass and an SSI of 10.
- “Viscosity index improver-F” comb polymer (Mw: 360,000, Mw / Mn: less than 2.00) having at least a structural unit derived from a macromonomer having Mn of 500 or more as the main resin component A viscosity index improver having a main resin content of 23% by mass and an SSI of 4.
- “Viscosity index improver-G” main agent containing a comb polymer (Mw: 410,000, Mw / Mn: 1.78) having at least a structural unit derived from a macromonomer having Mn of 500 or more as the main resin component A viscosity index improver having a resin concentration of 23% by mass and an SSI of 5.
- “Viscosity index improver-H” main agent containing a comb polymer (Mw: 480,000, Mw / Mn: 1.92) having at least a structural unit derived from a macromonomer having an Mn of 500 or more as a main resin component A viscosity index improver having a resin content concentration of 23 mass% and an SSI of 7.
- “Viscosity index improver-I” polymethacrylate (PMA) (Mw: 510,000, Mw / Mn: 3.19) as the main resin component, the main resin content concentration is 19% by mass, and the SSI is 30 A viscosity index improver.
- Viscosity index improver-J polymethacrylate (PMA) (Mw: 380,000, Mw / Mn: 2.71) as the main resin component, the main resin content concentration is 19% by mass, and the SSI is 30 A viscosity index improver.
- a product was prepared.
- the amount of “viscosity index improver-A to K” is an amount including not only the comb polymer or PMA as the main resin component but also diluent oil.
- Examples 9 to 16 and Comparative Examples 3 to 4 Lubricating oil composition so that SAE viscosity grade is "0W-16" by blending base oil, viscosity index improver, pour point depressant, and engine oil additive package shown in Table 2 A product was prepared.
- the blending amount of “viscosity index improvers-A to K” is an amount including not only the comb polymer or PMA which is the main resin component but also diluent oil.
- the lubricating oil compositions of Examples 1 to 16 which are one aspect of the present invention, have an engine temperature of 40 ° C. compared to the lubricating oil compositions of Comparative Examples 1 to 4. It can be seen that the driving torque improvement rate under the assumed low temperature range is high and the fuel saving performance is excellent.
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Abstract
Description
例えば、特許文献1には、潤滑油基油に、無灰分散剤、及びPSSI(永久せん断安定性指数)が所定の範囲のポリメタクリレート系の粘度指数向上剤等を含み、粘度指数と100℃におけるHTHS粘度(高温高せん断粘度)との比を所定の範囲に調整した内燃機関用潤滑油組成物が開示されている。
特許文献1には、当該内燃機関用潤滑油組成物が、従来のものに比べて、油温が80℃の条件においてトルク低減率が高く、高温領域下での省燃費性が良好である旨が示されている。
特許文献1においては、エンジンの暖気運転終了後を想定した80℃での省燃費性についての検討はあるものの、エンジン始動時を想定した低温領域下での省燃費性の検討がなされてない。また、本発明者らの検討によって、特許文献1に記載の内燃機関用潤滑油組成物は、エンジン始動時を想定した低温領域下において省燃費性が劣るという問題があることが判明した。
[1]前記基油と共に、櫛形ポリマーを含有し、SSI(せん断安定性指数)が30以下である粘度指数向上剤(A)を含み、
150℃におけるHTHS粘度(高温高せん断粘度)(T150)が1.6~2.9mPa・sであり、且つ、40℃における動粘度(V40)[mm2/s]と150℃におけるHTHS粘度(T150)[mPa・s]との比(V40/T150)が12.4以下である、潤滑油組成物。
[2]上記[1]に記載の潤滑油組成物を10~60℃の低温領域下で使用する、潤滑油組成物の使用方法。
[3]基油に、櫛形ポリマーを含有し、SSI(せん断安定性指数)が30以下である粘度指数向上剤(A)を配合し、
150℃におけるHTHS粘度(高温高せん断粘度)(T150)が1.6~2.9mPa・sであり、且つ、40℃における動粘度(V40)[mm2/s]と150℃におけるHTHS粘度(T150)[mPa・s]との比(V40/T150)が12.4以下となるような潤滑油組成物を調製する工程(I)を有する、潤滑油組成物の製造方法。
また、本明細書において、「150℃もしくは100℃におけるHTHS粘度」は、ASTM D 4741に準拠して測定された、150℃もしくは100℃における高温高せん粘度の値であって、具体的には、実施例に記載の測定方法により得られる値を意味する。
一方、「エンジン始動時を想定した低温領域下」とは、通常10~60℃(好ましくは20~60℃)の温度範囲の環境下を指す。
また、「アルカリ土類金属原子」としては、ベリリウム原子(Be)、マグネシウム原子(Mg)、カルシウム原子(Ca)、ストロンチウム原子(Sr)、及びバリウム原子(Ba)を指す。
本発明の潤滑油組成物は、基油と共に、櫛形ポリマーを含有し、SSI(せん断安定性指数)が30以下である粘度指数向上剤(A)を含み、150℃におけるHTHS粘度(高温高せん断粘度)(T150)が1.6~2.9mPa・sであり、且つ、40℃における動粘度(V40)[mm2/s]と150℃におけるHTHS粘度(T150)[mPa・s]との比(V40/T150)が12.4以下である。
当該HTHS粘度(T150)が1.6mPa・s未満であると、潤滑性能が低下する傾向があるため好ましくない。一方、当該HTHS粘度(T150)が2.9mPa・sを超えると、低温での粘度特性が低下する傾向にあると共に、省燃費性能が低下するため好ましくない。
上記観点から、本発明の一態様において、当該潤滑油組成物の150℃におけるHTHS粘度(T150)としては、好ましくは1.7~2.8mPa・s、より好ましくは1.8~2.8mPa・s、更に好ましくは1.9~2.7mPa・s、より更に好ましくは2.0~2.7mPa・sである。
なお、当該HTHS粘度(T150)は、エンジンの高速運転時の高温領域下での粘度として想定することもできる。つまり、得られた潤滑油組成物の150℃におけるHTHS粘度(T150)が上記範囲に属していれば、当該潤滑油組成物は、エンジンの高速運転時を想定した高温領域下での粘度等の各種性状が良好であるといえる。
本発明者らは、当該比(V40/T150)が、エンジン始動時を想定した低温領域下での省燃費性能の指標となることを見出し、本発明を完成させたものである。つまり、当該比(V40/T150)が12.4を超える潤滑油組成物は、エンジン始動時を想定した低温領域下での省燃費性能が不十分である。
上記観点から、本発明の一態様の潤滑油組成物の40℃における動粘度(V40)と150℃におけるHTHS粘度(T150)との比(V40/T150)としては、好ましくは12.2以下、より好ましくは12.0以下、更に好ましくは11.7以下、より更に好ましくは11.5以下である。
また、本発明の一態様の潤滑油組成物において、当該比(V40/T150)の下限値は特に制限はないが、当該比(V40/T150)は、通常6.00以上、好ましくは8.00以上である。
(a)粘度指数向上剤(A)の含有量を増やすことで、HTHS粘度(T150)は上昇する傾向にある。そのため、HTHS粘度(T150)の値は、粘度指数向上剤(A)の含有量を適宜調整することで、容易に調整できる。
(b)粘度指数向上剤(A)の含有量を増やすほど、動粘度(V40)も上昇する傾向にある。特に、櫛形ポリマーに該当しないPMA等の粘度指数向上剤やSSIの値が高い粘度指数向上剤を用いる場合、その傾向は顕著に現れる。
(c)櫛形ポリマーは、低温領域下においては、粘性が発現され難い性質を有する。そのため、粘度指数向上剤(A)中の櫛形ポリマーの含有量の割合を増やすことで、得られる潤滑油組成物の低温領域下の動粘度である動粘度(V40)の値は低くなり、上記比(V40/T150)を小さい値に調整し易くなる。
(d)一方、櫛形ポリマーは、高温領域下では、せん断を受けても低粘度化せずに、一定以上の粘度を維持し得る性質を有する。そのため、粘度指数向上剤(A)中の櫛形ポリマーの含有量の割合を増やすことで、粘度指数向上剤(A)の総量が比較的少なくても、HTHS粘度(T150)の値を高く調整し易い。
(e)分子量分布(Mw/Mn)が低い櫛形ポリマーほど、低温領域下及び高温領域下での上記性質が発現され易く、HTHS粘度(T150)や上記比(V40/T150)を上述の範囲に調整し易い傾向がある。
以下、本発明の一態様の潤滑油組成物に含まれる各成分について説明する。
本発明の一態様の潤滑油組成物に含まれる基油としては、鉱油であってもよく、合成油であってもよく、鉱油と合成油との混合油を用いてもよい。
鉱油としては、例えば、パラフィン基系、中間基系、ナフテン基系等の原油を常圧蒸留して得られる常圧残油;当該常圧残油を減圧蒸留して得られる留出油;当該留出油を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製等の精製処理の1つ以上の処理を施した鉱油及びワックス;フィッシャー・トロプシュ法等により製造されるワックス(GTLワックス(Gas To Liquids WAX))を異性化することで得られる鉱油等が挙げられる。
これらの中でも、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製等の精製処理の1つ以上の処理を施した鉱油及びワックスが好ましく、API(米国石油協会)基油カテゴリーのグループ2及びグループ3に分類される鉱油がより好ましく、当該グループ3に分類される鉱油が更に好ましい。
これらの合成油の中でも、ポリα-オレフィンが好ましい。
なお、本発明の一態様において、これらの基油は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
当該基油の100℃における動粘度が2.0mm2/s以上であれば、蒸発損失が少ないため好ましい。一方、当該基油の100℃における動粘度が20.0mm2/s以下であれば、粘性抵抗による動力損失を抑えることができ、燃費改善効果が得られるため好ましい。
なお、本発明の一態様の潤滑油組成物において、2種以上の基油を組み合わせた混合油を用いる場合、当該混合油の動粘度及び粘度指数が上記範囲であることが好ましい。
本発明の潤滑油組成物は、櫛形ポリマーを含有し、SSIが30以下である粘度指数向上剤(A)を含む。
本発明では、上記の粘度指数向上剤(A)を用いることで、エンジンの高速運転時を想定した高温領域下での粘度等の各種性状を良好に維持しつつ、エンジン始動時を想定した低温領域下での省燃費性能を向上させることができる。
なお、本明細書において、上記の「樹脂分」とは、重量平均分子量(Mw)が1000以上で、一定の繰り返し単位を有する重合体を意味する。
ただし、本発明の一態様の潤滑油組成物において、粘度指数向上剤のSSIの値を調整する観点、及びエンジン始動時を想定した低温領域下での省燃費性能を向上させる観点から、櫛形ポリマーには該当しない他の樹脂分(特に、ポリメタクリレート系化合物)の含有量は、少ない程好ましい。
櫛形ポリマーには該当しないポリメタクリレート系化合物の含有量は、上記観点から、潤滑油組成物中に含まれる櫛形ポリマー100質量部に対して、好ましくは0~30質量部、より好ましくは0~25質量部、更に好ましくは0~20質量部、より更に好ましくは0~15質量部である。
なお、上記の「粘度指数向上剤(A)中の固形分」とは、粘度指数向上剤(A)から希釈油を除いた成分を意味し、櫛形ポリマーだけでなく、上述の櫛形ポリマーには該当しない他の樹脂分や副生成物も含まれる。
本発明の一態様で用いる粘度指数向上剤(A)が上記溶液の形態である場合、当該溶液の前記固形分濃度としては、当該溶液の全量(100質量%)基準で、通常10~50質量%である。
なお、本明細書において、上記「粘度指数向上剤(A)の含有量」は、櫛形ポリマーや上述の他の樹脂分を含む固形分量であって、希釈油の質量は含まれない。
本明細書において、粘度指数向上剤(A)のSSIは、ASTM D6278に準拠して測定された値であって、具体的には、下記計算式(1)より算出された値である。
粘度指数向上剤(A)のSSIが30を超えると、エンジン始動時を想定した低温領域下での省燃費性能が不十分となる傾向にある。また、得られる潤滑油組成物について、経時によって、高温での粘度の低下を招き、部品の摩耗や損傷が生じ易くなる。
なお、粘度指数向上剤(A)のSSIの下限値としては、特に制限は無いが、粘度指数向上剤(A)のSSIは、通常1以上、好ましくは2以上である。
・一般的に粘度指数向上剤として使用されるPMA等のSSIの値は、高くなる傾向にある。
・粘度指数向上剤の分子量が小さくなる程、当該粘度指数向上剤のSSIが低くなる傾向にある。
・一方、本発明で用いる櫛形ポリマーは、その櫛形構造によりSSIの値が低くなる傾向にある。そのため、粘度指数向上剤(A)中の櫛形ポリマーの含有割合を増やすことで、粘度指数向上剤(A)のSSIの値は低くなる傾向にある。
・櫛形ポリマーの側鎖に該当するマクロモノマー(I’)に由来する構成単位(I)の含有量が多い櫛形ポリマーの含有割合が増加する程、SSIの値が低くなる傾向にある。
・高分子量の側鎖を有する櫛形ポリマーの含有割合が増加する程、SSIの値が低くなる傾向にある。
本発明で用いる粘度指数向上剤(A)が含有する「櫛形ポリマー」とは、高分子量の側鎖が出ている三叉分岐点を主鎖に数多くもつ構造を有するポリマーを指す。
このような構造を有する櫛形ポリマーとしては、マクロモノマー(I’)に由来する構成単位(I)を少なくとも有する重合体が好ましい。この構成単位(I)が、上記の「高分子量の側鎖」に該当する。
なお、本発明において、上記の「マクロモノマー」とは、重合性官能基を有する高分子量モノマーのことを意味し、末端に重合性官能基を有する高分子量モノマーであることが好ましい。
一方、櫛形ポリマーは、高温領域下では、主鎖が基油中に広がり易く、増粘しやすい性質が発現され、一定以上の粘度を維持し得る性質を有する。そのため、櫛形ポリマーを含有する潤滑油組成物のHTHS粘度(T150)の値が高くなり易い。
上記一般式(ii)中、R2は、炭素数2~4の直鎖又は分岐のアルキレン基を示し、具体的には、エチレン基、1,2-プロピレン基、1,3-プロピレン基、1,2-ブチレン基、1,3-ブチレン基、1,4-ブチレン基等が挙げられる。
上記一般式(iii)中、R3は、水素原子又はメチル基を示す。
また、R4は炭素数1~10の直鎖又は分岐のアルキル基を示し、具体的には、メチル基、エチル基,n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、イソペンチル基、t-ペンチル基、イソヘキシル基、t-ヘキシル基、イソヘプチル基、t-ヘプチル基、2-エチルヘキシル基、イソオクチル基、イソノニル基、イソデシル基等が挙げられる。
なお、上記一般式(i)~(iii)で表される繰り返し単位をそれぞれ複数有する場合には、R1、R2、R3、R4は、それぞれ同一であってもよく、互いに異なるものであってもよい。
また、本発明の一態様で用いる櫛形ポリマーは、マクロモノマー(I’)に由来する構成単位(I)と共に、マクロモノマー(I’)以外の他のモノマー(II’)に由来する構成単位(II)を含む共重合体であってもよい。
このような櫛形ポリマーの具体的な構造としては、モノマー(II’)に由来する構成単位(II)を含む主鎖に対して、マクロモノマー(I’)に由来する構成単位(I)を含む側鎖を有する共重合体が好ましい。
なお、本発明で用いる櫛形ポリマーにおいて、構成単位(II)の含有量が増えるほど、マクロモノマー(I’)に由来する高分子量の側鎖を有する主鎖の三叉分岐点間の距離が長くなる。その結果、低温領域下では低粘性となるため、動粘度(V40)の値を低く調整し易く、高温領域下では高粘度となるためHTHS粘度(T150)の値が高く調整し易くなる。
なお、モノマー(II’)としては、芳香族炭化水素系ビニル単量体(h)以外の単量体が好ましい。
R12は、単結合、炭素数1~10の直鎖又は分岐のアルキレン基、-O-、もしくは-NH-を示す。
R13は、炭素数2~4の直鎖又は分岐のアルキレン基を示す。また、nは1以上の整数(好ましくは1~20の整数、より好ましくは1~5の整数)を示す。なお、nが2以上の整数の場合、複数のR13は、同一であってもよく、異なっていてもよく、さらに、(R13O)n部分は、ランダム結合でもブロック結合でもよい。
R14は、炭素数1~60(好ましくは10~50、より好ましくは20~40)の直鎖又は分岐のアルキル基を示す。
上記の「炭素数1~10の直鎖又は分岐のアルキレン基」、「炭素数2~4の直鎖又は分岐のアルキレン基」、及び「炭素数1~60の直鎖又は分岐のアルキル基」の具体的な基としては、上述の一般式(i)~(iii)に関する記載で例示した基と同じものが挙げられる。
アルキル(メタ)アクリレート(b)としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソ-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、2-t-ブチルヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、3-イソプロピルヘプチル(メタ)アクリレート等が挙げられる。
アルキル(メタ)アクリレート(b)が有するアルキル基の炭素数としては、好ましくは1~30、より好ましくは1~26、更に好ましくは1~10である。
窒素原子含有ビニル単量体(c)としては、例えば、アミド基含有ビニル単量体(c1)、ニトロ基含有単量体(c2)、1級アミノ基含有ビニル単量体(c3)、2級アミノ基含有ビニル単量体(c4)、3級アミノ基含有ビニル単量体(c5)、及びニトリル基含有ビニル単量体(c6)等が挙げられる。
水酸基含有ビニル単量体(d)としては、例えば、ヒドロキシル基含有ビニル単量体(d1)、及びポリオキシアルキレン鎖含有ビニル単量体(d2)等が挙げられる。
リン原子含有単量体(e)としては、例えば、リン酸エステル基含有単量体(e1)、及びホスホノ基含有単量体(e2)等が挙げられる。
脂肪族炭化水素系ビニル単量体(f)としては、例えば、エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン及びオクタデセン等の炭素数2~20のアルケン;ブタジエン、イソプレン、1,4-ペンタジエン、1,6-ヘプタジエン及び1,7-オクタジエン等の炭素数4~12のアルカジエン;等が挙げられる。
脂肪族炭化水素系ビニル単量体(f)の炭素数としては、好ましくは2~30、より好ましくは2~20、更に好ましくは2~12である。
脂環式炭化水素系ビニル単量体(g)としては、例えば、シクロヘキセン、(ジ)シクロペンタジエン、ピネン、リモネン、ビニルシクロヘキセン及びエチリデンビシクロヘプテン等が挙げられる。
脂環式炭化水素系ビニル単量体(g)の炭素数としては、好ましくは3~30、より好ましくは3~20、更に好ましくは3~12である。
芳香族炭化水素系ビニル単量体(h)としては、例えば、スチレン、α-メチルスチレン、α-エチルスチレン、ビニルトルエン、2,4-ジメチルスチレン、4-エチルスチレン、4-イソプロピルスチレン、4-ブチルスチレン、4-フェニルスチレン、4-シクロヘキシルスチレン、4-ベンジルスチレン、p-メチルスチレン、モノクロロスチレン、ジクロロスチレン、トリブロモスチレン、テトラブロモスチレン、4-クロチルベンゼン、インデン及び2-ビニルナフタレン等が挙げられる。
芳香族炭化水素系ビニル単量体(h)の炭素数としては、好ましくは8~30、より好ましくは8~20、更に好ましくは8~18である。
ビニルエステル類(i)としては、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル及びオクタン酸ビニル等の炭素数2~12の飽和脂肪酸のビニルエステル等が挙げられる。
ビニルエーテル類(j)としては、例えば、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、及び2-エチルヘキシルビニルエーテル等の炭素数1~12のアルキルビニルエーテル;フェニルビニルエーテル等の炭素数6~12のアリールビニルエーテル;ビニル-2-メトキシエチルエーテル、及びビニル-2-ブトキシエチルエーテル等の炭素数1~12のアルコキシアルキルビニルエーテル;等が挙げられる。
ビニルケトン類(k)としては、例えば、メチルビニルケトン、及びエチルビニルケトン等の炭素数1~8のアルキルビニルケトン;フェニルビニルケトン等の炭素数6~12のアリールビニルケトン等が挙げられる。
エポキシ基含有ビニル単量体(l)としては、例えば、グリシジル(メタ)アクリレート、グリシジル(メタ)アリルエーテル等が挙げられる。
ハロゲン元素含有ビニル単量体(m)としては、例えば、塩化ビニル、臭化ビニル、塩化ビニリデン、塩化(メタ)アリル及びハロゲン化スチレン(ジクロロスチレン等)等が挙げられる。
不飽和ポリカルボン酸のエステル(n)としては、例えば、不飽和ポリカルボン酸のアルキルエステル、不飽和ポリカルボン酸のシクロアルキルエステル、不飽和ポリカルボン酸のアラルキルエステル等が挙げられ、不飽和カルボン酸としては、例えば、マレイン酸、フマール酸、イタコン酸等が挙げられる。
(ジ)アルキルフマレート(o)としては、例えば、モノメチルフマレート、ジメチルフマレート、モノエチルフマレート、ジエチルフマレート、メチルエチルフマレート、モノブチルフマレート、ジブチルフマレート、ジペンチルフマレート、ジヘキシルフマレート等が挙げられる。
(ジ)アルキルマレエート(p)としては、例えば、モノメチルマレエート、ジメチルマレエート、モノエチルマレエート、ジエチルマレエート、メチルエチルマレエート、モノブチルマレエート、ジブチルマレエート等が挙げられる。
当該櫛形ポリマーの分子量分布が小さくなる程、低温領域下及び高温領域下での上述の櫛形ポリマーの性質が発現され易く、HTHS粘度(T150)や上記比(V40/T150)を上述の範囲に調整し易い。そのため、分子量分布が小さい櫛形ポリマーを含む潤滑油組成物は、エンジン始動時を想定した低温領域下での省燃費性能をより向上させたものとなり得る。
また、櫛形ポリマーの分子量分布の下限値としては特に制限はないが、櫛形ポリマーの分子量分布(Mw/Mn)としては、通常1.01以上、好ましくは1.05以上、より好ましくは1.10以上である。
なお、本明細書において、上記「櫛形ポリマーの含有量」には、当該櫛形ポリマーと共に含有される場合がある希釈油等の質量は含まれない。
本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、必要に応じて、さらに粘度指数向上剤以外の潤滑油用添加剤を含有してもよい。
当該潤滑油用添加剤としては、例えば、金属系清浄剤、分散剤、耐摩耗剤、極圧剤、酸化防止剤、流動点降下剤、消泡剤、摩擦調整剤、防錆剤、金属不活性化剤等が挙げられる。
これらの中でも、金属系清浄剤、分散剤、耐摩耗剤、極圧剤、酸化防止剤、流動点降下剤、及び消泡剤から選ばれる1種以上の潤滑油用添加剤を含有することが好ましい。
なお、当該潤滑油用添加剤として、API/ILSAC規格やSN/GF-5規格等に適合した、複数の添加剤を含有する混合物である市販品の添加剤パーケージを用いてもよい。
なお、本発明の一態様の潤滑油組成物において、これらの潤滑油用添加剤の合計含有量は、当該潤滑油組成物の全量(100質量%)基準で、好ましくは30質量%以下、より好ましくは25質量%以下、更に好ましくは20質量%以下、より更に好ましくは15質量%以下である。
金属系清浄剤としては、例えば、アルカリ金属原子及びアルカリ土類金属原子から選ばれる金属原子を含有する有機金属系化合物が挙げられ、具体的には、金属サリシレート、金属フェネート、及び金属スルホネート等が挙げられる。
金属系清浄剤に含まれる金属原子としては、高温での清浄性の向上の観点から、ナトリウム原子、カルシウム原子、マグネシウム原子、又はバリウム原子が好ましく、カルシウム原子がより好ましい。
Rとして選択し得る炭化水素基としては、例えば、炭素数1~18のアルキル基、炭素数1~18のアルケニル基、環形成炭素数3~18のシクロアルキル基、環形成炭素数6~18のアリール基、炭素数7~18のアルキルアリール基、炭素数7~18のアリールアルキル基等が挙げられる。
これらの中でも、高温での清浄性の向上の観点、及び基油への溶解性の観点から、カルシウムサリシレート、カルシウムフェネート、及びカルシウムスルホネートから選ばれる1種以上であることが好ましい。
本発明の一態様で用いる金属系清浄剤が塩基性塩又は過塩基性塩である場合、当該金属系清浄剤の塩基価としては、好ましくは10~600mgKOH/g、より好ましくは20~500mgKOH/gである。
なお、本明細書において、「塩基価」とは、JIS K2501「石油製品および潤滑油-中和価試験方法」の7.に準拠して測定される過塩素酸法による塩基価を意味する。
分散剤としては、例えば、コハク酸イミド、ベンジルアミン、コハク酸エステル又はこれらのホウ素変性物等が挙げられる。
コハク酸イミドとしては、例えば、分子量300~4,000のポリブテニル基等のポリアルケニル基を有するコハク酸と、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等のポリエチレンポリアミンのモノイミド又はビスイミド、若しくはこれらのホウ酸変性物;ポリアルケニル基を有するフェノールとホルムアルデヒドとポリエチレンポリアミンのマンニッヒ反応物等が挙げられる。
耐摩耗剤又は極圧剤としては、例えば、ジアルキルジチオリン酸亜鉛(ZnDTP)、リン酸亜鉛、ジチオカルバミン酸亜鉛、ジチオカルバミン酸モリブデン、ジチオリン酸モリブデン、ジスルフィド類、硫化オレフィン類、硫化油脂類、硫化エステル類、チオカーボネート類、チオカーバメート類、ポリサルファイド類等の硫黄含有化合物;亜リン酸エステル類、リン酸エステル類、ホスホン酸エステル類、及びこれらのアミン塩又は金属塩等のリン含有化合物;チオ亜リン酸エステル類、チオリン酸エステル類、チオホスホン酸エステル類、及びこれらのアミン塩又は金属塩等の硫黄及びリン含有耐摩耗剤が挙げられる。
これらの中でも、ジアルキルジチオリン酸亜鉛(ZnDTP)が好ましい。
極圧剤としては、例えば、スルフィド類、スルフォキシド類、スルフォン類、チオホスフィネート類等の硫黄系極圧剤、塩素化炭化水素等のハロゲン系極圧剤、有機金属系極圧剤等が挙げられる。
酸化防止剤としては、従来潤滑油の酸化防止剤として使用されている公知の酸化防止剤の中から、任意のものを適宜選択して用いることができ、例えば、アミン系酸化防止剤、フェノール系酸化防止剤、モリブデン系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤等が挙げられる。
アミン系酸化防止剤としては、例えばジフェニルアミン、炭素数3~20のアルキル基を有するアルキル化ジフェニルアミン等のジフェニルアミン系酸化防止剤;α-ナフチルアミン、炭素数3~20のアルキル置換フェニル-α-ナフチルアミン等のナフチルアミン系酸化防止剤;等が挙げられる。
フェノール系酸化防止剤としては、例えば、2,6-ジ-tert-ブチル-4-メチルフェノール、2,6-ジ-tert-ブチル-4-エチルフェノール、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート等のモノフェノール系酸化防止剤;4,4’-メチレンビス(2,6-ジ-tert-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-tert-ブチルフェノール)等のジフェノール系酸化防止剤;ヒンダードフェノール系酸化防止剤;等を挙げられる。
モリブデン系酸化防止剤としては、例えば、三酸化モリブデン及び/又はモリブデン酸とアミン化合物とを反応させてなるモリブデンアミン錯体等が挙げられる。
硫黄系酸化防止剤としては、例えば、ジラウリル-3,3’-チオジプロピオネイト等が挙げられる。
リン系酸化防止剤としては、例えば、ホスファイト等が挙げられる。
これらの酸化防止剤は、1種単独で又は2種以上を組み合わせて用いてもよいが、通常2種以上を組み合わせて使用するのが好ましい。
流動点降下剤としては、例えば、エチレン-酢酸ビニル共重合体、塩素化パラフィンとナフタレンとの縮合物、塩素化パラフィンとフェノールとの縮合物、ポリメタクリレート、ポリアルキルスチレン等が挙げられる。
消泡剤としては、例えば、シリコーン油、フルオロシリコーン油およびフルオロアルキルエーテル等が挙げられる。
摩擦調整剤としては、例えば、ジチオカルバミン酸モリブデン(MoDTC)、ジチオリン酸モリブデン(MoDTP)、モリブテン酸のアミン塩等のモリブデン系摩擦調整剤;炭素数6~30のアルキル基又はアルケニル基を分子中に少なくとも1個有する、脂肪族アミン、脂肪酸エステル、脂肪酸アミド、脂肪酸、脂肪族アルコール、脂肪族エーテル等の無灰摩擦調整剤;等が挙げられる。
防錆剤としては、例えば、石油スルフォネート、アルキルベンゼンスルフォネート、ジノニルナフタレンスルフォネート、アルケニルコハク酸エステル、多価アルコールエステル等が挙げられる。
金属不活性化剤としては、例えば、ベンゾトリアゾール系化合物、トリルトリアゾール系化合物、チアジアゾール系化合物、イミダゾール系化合物、ピリミジン系化合物等が挙げられる。
本発明の潤滑油組成物は、エンジンの高速運転時を想定した高温領域下での粘度等の各種性状を良好としながらも、エンジン始動時を想定した低温領域下での省燃費性能に優れる。
そのため、本発明の潤滑油組成物を充填したエンジンは、高速運転時だけでなく、エンジン始動時の低温領域下での使用時においても省燃費性能に優れたものとなり得る。当該エンジンとしては、特に制限はないが、自動車用エンジンが好適である。
なお、上記の低温領域下の温度としては、エンジン始動時を想定した温度範囲であって、通常10~60℃であり、好ましくは20~60℃である。
本発明の一態様の潤滑油組成物について考え得る他の用途としては、例えば、パワーステアリングオイル、自動変速機油(ATF)、無段変速機油(CVTF)、油圧作動油、タービン油、圧縮機油、工作機械用潤滑油、切削油、歯車油、流体軸受け油、転がり軸受け油等が挙げられる。
本発明は、以下の工程(I)を有する潤滑油組成物の製造方法も提供する。
工程(I):基油に、櫛形ポリマーを含有し、SSI(せん断安定性指数)が30以下である粘度指数向上剤(A)を配合し、
150℃におけるHTHS粘度(高温高せん断粘度)(T150)が1.6~2.9mPa・sであり、且つ、40℃における動粘度(V40)[mm2/s]と150℃におけるHTHS粘度(T150)[mPa・s]との比(V40/T150)が12.4以下となるような潤滑油組成物を調製する工程。
また、本工程において、基油及び成分(A)以外の上述の潤滑油用添加剤等を配合してもよい。
本発明の一態様において、成分(A)を固形分濃度が10~50質量%の粘度指数向上剤(A)の溶液の形態で配合する場合、当該溶液の配合量としては、当該潤滑油組成物の全量(100質量%)に対して、好ましくは0.1~30質量%、より好ましくは1~25質量%、更に好ましくは2~20質量%である。
各成分を配合した後、公知の方法により、撹拌して均一に分散させることが好ましい。
なお、各成分を配合後に、成分の一部が変性したり、2成分が互いに反応し、別の成分を生成した場合の得られる潤滑油組成物についても、本発明の技術的範囲に属するものである。
ゲル浸透クロマトグラフ装置(アジレント社製、「1260型HPLC」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(測定条件)
・カラム:「Shodex LF404」を2本順次連結したもの
・カラム温度:35℃
・展開溶媒:クロロホルム
・流速:0.3mL/min
ASTM D6278に準拠して測定した。具体的には、対象となる粘度指数向上剤について、前記計算式(1)中のKv0、Kv1、Kvoilの各値を測定して、当該計算式(1)より算出した。
JIS K 2283に準拠して測定した。
(4)粘度指数
JIS K 2283に準拠して測定した。
(5)100℃及び150℃のHTHS粘度(高温高せん断粘度)
ASTM D 4741に準拠して、対象となる潤滑油組成物を、100℃又は150℃で、せん断速度106/sにて、せん断した後の粘度を測定した。
排気量1.5LのSOHC(Single OverHead Camshaft)エンジンのメインシャフトをモーターで駆動し、その際にカム軸にかかるトルクを測定した。カム軸の回転数は、1,500rpm、エンジン油温及び水温は40℃とした。
実施例1~8及び比較例1~3では、比較例1の潤滑油組成物を用いたときのトルクの測定値を基準として、実施例9~16及び比較例4~6では、比較例4の潤滑油組成物を用いたときのトルクの測定値を基準として、下記式から駆動トルク改善率(%)を算出し、評価した。
・駆動トルク改善率(%)=([評価対象の潤滑油組成物のトルクの測定値]-[比較例1又は4の潤滑油組成物のトルクの測定値])/[比較例1又は4の潤滑油組成物のトルクの測定値]×100
数字が大きいほど駆動トルクが改善され、省燃費性が高いことを示す。
<基油>
・「100N鉱油」=40℃動粘度:17.8mm2/s、100℃動粘度:4.07mm2/s、粘度指数:131、密度:0.824g/cm3。
・「70N鉱油」=40℃動粘度:12.5mm2/s、100℃動粘度:3.12mm2/s、粘度指数:110、密度:0.832g/cm3。
・「粘度指数向上剤-A」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:25万、Mw/Mn:2.08)を含む、主剤樹脂分濃度が19質量%、SSIが3である粘度指数向上剤。
・「粘度指数向上剤-B」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:42万、Mw/Mn:5.92)を含む、主剤樹脂分濃度が19質量%、SSIが5である粘度指数向上剤。
・「粘度指数向上剤-C」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:33万、Mw/Mn:2.00以上)を含む、主剤樹脂分濃度が25質量%、SSIが5である粘度指数向上剤。
・「粘度指数向上剤-D」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:44万、Mw/Mn:2.00以上)を含む、主剤樹脂分濃度が25質量%、SSIが8である粘度指数向上剤。
・「粘度指数向上剤-E」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:48万、Mw/Mn:2.00以上)を含む、主剤樹脂分濃度が25質量%、SSIが10である粘度指数向上剤。
・「粘度指数向上剤-F」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:36万、Mw/Mn:2.00未満)を含む、主剤樹脂分濃度が23質量%、SSIが4である粘度指数向上剤。
・「粘度指数向上剤-G」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:41万、Mw/Mn:1.78)を含む、主剤樹脂分濃度が23質量%、SSIが5である粘度指数向上剤。
・「粘度指数向上剤-H」=主剤樹脂分として、Mnが500以上のマクロモノマーに由来する構成単位を少なくとも有する櫛形ポリマー(Mw:48万、Mw/Mn:1.92)を含む、主剤樹脂分濃度が23質量%、SSIが7である粘度指数向上剤。
・「粘度指数向上剤-I」=主剤樹脂分として、ポリメタクリレート(PMA)(Mw:51万、Mw/Mn:3.19)を含む、主剤樹脂分濃度が19質量%、SSIが30である粘度指数向上剤。
・「粘度指数向上剤-J」=主剤樹脂分として、ポリメタクリレート(PMA)(Mw:38万、Mw/Mn:2.71)を含む、主剤樹脂分濃度が19質量%、SSIが30である粘度指数向上剤。
・「PMA系流動点降下剤」=Mw:6.2万のポリメタアクリレート系流動点降下剤。
<各種添加剤>
・「エンジン油用添加剤パッケージ」:API/ILSAC規格、及びSN/GF-5規格に適合した添加剤パーケージであり、以下の各種添加剤等を含む。
金属系清浄剤:過塩基性カルシウムサリチレート
分散剤:高分子ビスイミド、ホウ素変性モノイミド
耐摩耗剤:第1級のZnDTP、及び第2級のZnDTP
酸化防止剤:ジフェニルアミン系酸化防止剤、ヒンダードフェノール系酸化防止剤、モリブデン系酸化防止剤
消泡剤:シリコン系消泡剤
表1に示す種類及び配合量の基油、粘度指数向上剤、流動点降下剤、及びエンジン油用添加剤パッケージを配合して、SAE粘度グレードが「0W-20」となるように潤滑油組成物を調製した。なお、表1中の「粘度指数向上剤-A~K」の配合量は、主剤樹脂分である櫛形ポリマー又はPMAだけでなく、希釈油等も含めた量である。
そして、調製した潤滑油組成物について、上記の方法に基づき、40℃及び100℃における動粘度、粘度指数、100℃及び150℃におけるHTHS粘度、並びに、駆動トルク改善率(比較例1を基準)をそれぞれ測定した。これらの測定結果を表1に示す。
表2に示す種類及び配合量の基油、粘度指数向上剤、流動点降下剤、及びエンジン油用添加剤パッケージを配合して、SAE粘度グレードが「0W-16」となるように潤滑油組成物を調製した。なお、表2中の「粘度指数向上剤-A~K」の配合量は、主剤樹脂分である櫛形ポリマー又はPMAだけでなく、希釈油等も含めた量である。
そして、調製した潤滑油組成物について、上記の方法に基づき、40℃及び100℃の動粘度、粘度指数、100℃及び150℃のHTHS粘度、並びに、駆動トルク改善率(比較例4を基準)をそれぞれ測定した。これらの測定結果を表2に示す。
Claims (16)
- 基油と共に、櫛形ポリマーを含有し、SSI(せん断安定性指数)が30以下である粘度指数向上剤(A)を含み、
150℃におけるHTHS粘度(高温高せん断粘度)(T150)が1.6~2.9mPa・sであり、且つ、40℃における動粘度(V40)[mm2/s]と150℃におけるHTHS粘度(T150)[mPa・s]との比(V40/T150)が12.4以下である、潤滑油組成物。 - 前記櫛形ポリマーの含有量が、前記潤滑油組成物の全量基準で、0.01~10.00質量%である、請求項1に記載の潤滑油組成物。
- 前記櫛形ポリマーの重量平均分子量(Mw)が、1万~100万である、請求項1又は2に記載の潤滑油組成物。
- 前記櫛形ポリマーの分子量分布(Mw/Mn)(但し、Mwは当該櫛形ポリマーの重量平均分子量、Mnは当該櫛形ポリマーの数平均分子量を示す)が、6.00以下である、請求項1~3のいずれか1項に記載の潤滑油組成物。
- 前記櫛形ポリマーが、マクロモノマー(I’)に由来する構成単位(I)を少なくとも有する重合体である、請求項1~4のいずれか1項に記載の潤滑油組成物。
- さらに、金属系清浄剤、分散剤、耐摩耗剤、極圧剤、酸化防止剤、流動点降下剤、及び消泡剤から選ばれる1種以上の潤滑油用添加剤を含む、請求項1~5のいずれか1項に記載の潤滑油組成物。
- 前記金属系清浄剤が、アルカリ金属原子及びアルカリ土類金属原子から選ばれる金属原子を含有する有機金属系化合物である、請求項6に記載の潤滑油組成物。
- 前記基油の100℃における動粘度が、2.0~20.0mm2/sである、請求項1~7のいずれか1項に記載の潤滑油組成物。
- 前記基油が、API(米国石油協会)基油カテゴリーでグループ2及びグループ3に分類される鉱油、並びに合成油から選ばれる1種以上である、請求項1~8のいずれか1項に記載の潤滑油組成物。
- 100℃における動粘度(V100)が、4.0~12.5mm2/sである、請求項1~9のいずれか1項に記載の潤滑油組成物。
- 40℃における動粘度(V40)が、10.0~40.0mm2/sである、請求項1~10のいずれか1項に記載の潤滑油組成物。
- 粘度指数が140以上である、請求項1~11のいずれか1項に記載の潤滑油組成物。
- 櫛形ポリマーには該当しないポリメタクリレート系化合物の含有量が、前記潤滑油組成物中に含まれる櫛形ポリマー100質量部に対して、0~30質量部である、請求項1~12のいずれか1項に記載の潤滑油組成物。
- 粘度指数向上剤(A)中の櫛形ポリマーの含有量が、粘度指数向上剤(A)中の固形分の全量(100質量%)基準で、60~100質量%である、請求項1~13のいずれか1項に記載の潤滑油組成物。
- 請求項1~14のいずれか1項に記載の潤滑油組成物を10~60℃の低温領域下で使用する、潤滑油組成物の使用方法。
- 基油に、櫛形ポリマーを含有し、SSI(せん断安定性指数)が30以下である粘度指数向上剤(A)を配合し、
150℃におけるHTHS粘度(高温高せん断粘度)(T150)が1.6~2.9mPa・sであり、且つ、40℃における動粘度(V40)[mm2/s]と150℃におけるHTHS粘度(T150)[mPa・s]との比(V40/T150)が12.4以下となるような潤滑油組成物を調製する工程(I)を有する、潤滑油組成物の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/318,837 US10472583B2 (en) | 2014-09-19 | 2015-09-18 | Lubricating oil composition |
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JP2017171864A (ja) * | 2016-03-25 | 2017-09-28 | 出光興産株式会社 | 潤滑油組成物、内燃機関、及び内燃機関の潤滑方法 |
WO2018091595A1 (en) * | 2016-11-17 | 2018-05-24 | Shell Internationale Research Maatschappij B.V. | Lubricating oil composition |
WO2018174126A1 (ja) * | 2017-03-23 | 2018-09-27 | 出光興産株式会社 | 潤滑油組成物 |
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US10472583B2 (en) | 2019-11-12 |
KR102497375B1 (ko) | 2023-02-07 |
JPWO2016043334A1 (ja) | 2017-04-27 |
JP6144844B2 (ja) | 2017-06-07 |
US20170137732A1 (en) | 2017-05-18 |
KR20170063575A (ko) | 2017-06-08 |
CN106459821A (zh) | 2017-02-22 |
CN106459821B (zh) | 2021-01-22 |
EP3196279A1 (en) | 2017-07-26 |
EP3196279A4 (en) | 2018-07-25 |
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