Classifications

• • 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
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/135—Steam engines or turbines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

• the present invention relates to a lubricating oil composition having a high viscosity index, excellent low- temperature flowability, and a high flash point, and which can be satisfactorily used as a hydraulic oil, turbine oil, compressor oil, machine-tool lubricating oil, gear oil and so on.
• the viscosity is generally lower the higher the temperature, but it is desirable in practice that as far as possible there should be no variation in viscosity over a wide range from low
• the viscosity index (VI) is an indicator of the resistance to change in viscosity due to temperature change, and the higher its value the smaller the change in viscosity due to temperature change.
• a desirable VI is regarded as being not less than 180, but more preferably not less than 200.
• Japanese laid-open Patent 2009-96995 which is based on the Inventors' work
• flowability improvers additives intended to improve low-temperature flowability
• base oils of lubricating oil compositions to which flowability improvers are added are manufactured under various manufacturing conditions depending on the raw materials and plant apparatus, there are naturally many and various kinds of these.
• flowability improvers additives intended to improve low-temperature flowability
• the aim of this invention is therefore to offer a lubricating oil composition which will satisfy the practical performance requirements as regards all of viscosity index, low-temperature flowability and flash point .
• a lubricating oil composition comprising a base oil having a kinematic viscosity at 100°C in the range of from 3 to 6 mm 2 /s and not less than 18% by mass of flowability improver having a peak-top temperature measured by DSC of not less than 13°C lower than the crystallisation onset temperature measured by DSC of the base oil, wherein the lubricating oil composition has a kinematic viscosity at 100°C in the range of from 9.3 to 12.5 mm 2 /s, a viscosity index of not less than 200, a pour point of -40°C or lower, and a flash point of not less than 200°C.
• Lubricating oils including hydraulic oils, are mostly classified into Class III Petroleum and Class IV Petroleum of Hazardous Materials Category IV in fire- safety laws.
• the classification criterion is a flash point of not less than 70°C but less than 200°C, and in the case of a Class IV Petroleum of Category IV a flash point of not less than 200°C.
• the lubricating oil composition of this invention also requires the flash point to be not less than 200°C.
• the kinematic viscosity at 100°C must be within the scope of SAE30 of the SAE viscosity classification, or more specifically from 9.3 to 12.5 mm 2 /s.
• DSC differential scanning calorimetry
• Temperature conditions After holding for 2 minutes at 50°C, holding for 2 minutes at - 60°C, then holding for 5 minutes again at 50°C
• Temperature correction samples Sn, In, n-tridecan.
• Crystalstallisation onset temperature means the temperature, in the transitions due to change of heat flow relative to the temperature measured by DSC, when it begins a transition which is different from the previous one, and it is obtained by the method described in JIS K 7121 9.2 "Methods of Obtaining
• Crystallisation Onset Temperature It may, for example, also be taken as the temperature when the measured heat flow becomes greater than 0, but if the changes over time of the amount of heat put out are small, in other words if the period the heat is put out is long and a broad peak appears, or if the changes over time for the amount of heat put out are large, in other words if the
• crystallization onset temperature is preferably taken as the intersection of the tangent of the point of
• peak-top temperature means the temperature where the heat flow is largest in the transition due to change in heat flow relative to the temperature measured by the aforementioned DSC.
• crystallisation onset temperature and the peak-top temperature as measured by DSC of the base oil and flowability improver More specifically, it is possible to achieve a viscosity index of not less than 200, a pour point of -40°C or lower, and a flash point of not less than 200°C.
• the pour point is being reduced, it is only natural that it is preferable to use a base oil and a flowability improver where both have a low pour point, but it has already been said that there is a problem in that this invites a reduction of the flash point in low- viscosity base oils with a low pour point.
• using a base oil and a flowability improver with low pour points involves an increase in cost.
• excessive low- temperature flowability is not necessary, and if it gives performance to a degree that matches the consumer's requirements, specifically, say, a pour point of about - 40°C, it can withstand use well enough.
• the lubricating oil composition of this invention can be blended by taking this sort of problem into account. Specifically, it is possible first to determine a base oil in order to clear the target pour point, for example -40°C, and, taking the crystallisation onset temperature thereof as the criterion, to pare down candidates for the
• base oils are marketed with viscosities such as SAE10, SAE20, SAE30 and SAE40, but when incorporating additives the need arises to regulate the viscosities by blending a plurality of base oils with different viscosities as appropriate to the viscosities of the additives, so that there have been many base oil mixtures. Therefore, in the past, as regards the finally blended product, there has been the need to confirm the flowability again.
• the kinematic viscosity @ 100°C for the base oil is in the range of from 3 to 6 mm 2 /s. If it is less than 3 mm 2 /s, a fire-prevention problem will arise owing to a reduction in the flash point and a problem will arise with a reduction in shear stability. If it is greater than 6 mm 2 /s, the pour point will increase and there will be a problem in that low- temperature flowability will be degraded.
• base oil in the lubricating oil composition of the present invention it is possible to use the mineral oils, synthetic oils or mixtures thereof used in normal lubricating oils, and it possible to use, singly or as mixtures, base oils which belong to Group I, Group II, Group III, Group IV and Group V of the API (American Petroleum Institute) base oil categories.
• Group I base oils include, for example, paraffinic mineral oils obtained by a suitable combination of refining processes such as solvent refining,
• the viscosity index should be in the range of from 80 to less than 120 and preferably in the range of from 95 to 110.
• the kinematic viscosity at 40°C should be in the range of from 80 to less than 120 and preferably in the range of from 95 to 110.
• the total sulphur content should be less than 1.5% by mass and preferably less than 1.0% by mass.
• the total nitrogen content should be less than 50 ppm and
• oils with an aniline point in the range of from 80 to 150°C and preferably in the range of from 90 to 120°C should be used .
• Group II base oils include, for example, paraffinic mineral oils obtained by a suitable combination of refining processes such as hydrocracking and dewaxing in respect of lubricating oil fractions obtained by
• Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of not more than 5% and so can be used for this invention.
• the viscosity of these base oils is not specially limited, but the viscosity index should be in the range of from 80 to less than 120 and
• the kinematic viscosity at 40°C should preferably be in the range of from 2 to 680 mm 2 /s and more preferably in the range of from 8 to 220 mm 2 /s.
• the total sulphur content should be less than 300 ppm, preferably less than 50 ppm and more preferably less than 10 ppm.
• the total nitrogen content should also be less than 10 ppm and preferably less than 1 ppm.
• oils with an aniline point in the range of from 80 to 150°C and preferably in the range of from 100 to 135°C should be used.
• Group III base oils include, for example, paraffinic mineral oils manufactured by a high degree of
• the viscosity of these base oils is not specially limited, but the viscosity index should be not less than 120, and preferably in the range of from 120 to 140.
• the kinematic viscosity at 40°C should preferably be in the range of from 2 to 680 mm 2 /s and more preferably in the range of from 8 to 220 mm 2 /s.
• the total sulphur content should be less than 100 ppm and preferably less than 10 ppm.
• the total nitrogen content should also be less than 10 ppm and preferably less than 1 ppm.
• oils with an aniline point in the range of from 80 to 150°C and preferably in the range of from 110 to 135°C should be used.
• polyolefins include polyolefins.
• Said polyolefins include polyolefins.
• polymers of various olefins and hydrides thereof Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and -olefins with 5 or more carbon atoms.
• olefins it is possible to use one kind or combinations of two or more kinds of the aforementioned olefins.
• PAO poly- -olefins
• the viscosities of these synthetic base oils is not specially limited, but the kinematic viscosity at 40°C should preferably be in the range of from 2 to 680 mm 2 /s and more preferably in the range of from 8 to 220 mm 2 / s .
• Group V base oils are esters and other base oils that do not belong to Groups I to IV.
• Table 1 shows typical examples of the properties of the various base oils in the API classification.
• crystallisation onset temperature of the base oil as measured by DSC is not less than 13°C.
• the crystallization onset temperature of the fluidity improver used in the present invention is not more than -23°C, preferably not more than -25°C, more preferably not more than -27°C.
• flowability improver is not more than -35°C, preferably not more than -40°C, more preferably not more than -45°C.
• the mass-average molecular weight of the fluidity improver is not more than 55,000, preferably less than
• Lubricating oil compositions were prepared using the base oils shown in Table 3 and the flowability improvers (hereinafter “polymers”) shown in Table 4 below.
• Crystallisation Onset Temperature The crystallisation onset temperature was obtained in accordance with JIS K 7121 9.2 "Methods of Obtaining Temperature of Crystallisation, (2) Extrapolated
• DSC6200 (commercial name, made by SII Ltd)
• the mass average molecular weight was calculated based on "JIS K7252-1 Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 1 General principles"
• Carrier Flow rate 0.8ml/min (Ref. 0.3ml/min)
• Amount of sample injection 50 ⁇
• the pour point, viscosity and flash point of the prepared lubricating compositions were measured.
• the measured values and the calculated values are shown in Table 5.
• the hydraulic oil package included, as the additives, a metallic detergent, an anti-wear agent, an amine-based anti-oxidant , a phenolic anti- oxidant, a corrosion inhibitor, a defoaming agent and a metal deactivator.
• Example 1 was a base oil mixture of Base Oil A and Base Oil B blended in the respective proportions of 34.00% by mass and 42.50% by mass. Recalculating on the basis of the mixing
• Example 2 it was 21.7°C, in Comparative Example 1 it was 2.3°C, in Comparative Example 2 it was 12.7°C, in Comparative Example 3 it was 4.6°C, in
• Example 5 it was 29.4°C. On the basis of these results it was possible to achieve a pour point of -40°C by adding at least not less than 18% by mass of a flowability improver with a Bs - Pt of not less than 13°C to a base oil having a kinematic viscosity at 100°C in the range of from 3 to 6 mm 2 /s.
• the flash point in all of the aforementioned examples and comparative examples was not less than 200°C, they clearly satisfy the flash point requirements for hydraulic oils used in construction, in addition to the aforementioned requirements for pour point and viscosity index in the case of base oils having a kinematic viscosity at 100° in the range of from 3 to 6 mm 2 / s .

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• 2011
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