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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/04—Hydroxy compounds
  • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
• • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/68—Esters
  • C10M129/76—Esters containing free hydroxy or carboxyl groups
• • 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
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
• • 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
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/18—Complexes with metals
• • 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
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • 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
  • C10M2203/02—Well-defined aliphatic compounds
  • C10M2203/0206—Well-defined aliphatic compounds 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
  • C10M2215/065—Phenyl-Naphthyl amines
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • 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
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/09—Complexes with metals
• • 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
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/12—Groups 6 or 16
• • 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
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • 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
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
• • 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
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • 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
  • C10N2030/40—Low content or no content compositions
  • C10N2030/45—Ash-less or low ash content
• • 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
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to a lubricating oil composition.
• a lubricating oil composition useful for internal combustion engines is provided which composition is phosphorus-free, said composition comprising at least 60% wt. of base oil selected from the group consisting of Group I, Group II, Group III and Group IV base oils or mixtures thereof, and at least 1.4% wt. of at least one antioxidant selected from the group consisting of aminic antioxidants, phenolic antioxidants and mixtures thereof, based on the total weight of the lubricating oil composition.
• a method of lubricating an internal engine using such lubricating oil composition is also provided.
• a lubricating oil composition which is suitable for lubricating camless internal combustion engines is provided.
• ZnDTP contributes to the sulphated ash content, sulphur content and phosphorus content in a lubricating oil composition.
• a lubricating oil composition In view of the adverse affects that the sulphated ash, sulphur and phosphorus concentrations of lubricating oil compositions may have on vehicle exhaust after-treatment devices, it may be desirable to develop lubricating oil compositions with reduced sulphated ash, sulphur and/or phosphorus concentrations therein.
• reducing or avoiding the use of ZnDTP in lubricating oil compositions is a method to reduce the sulphur and phosphorus content therein.
• anti-wear films developed by ZnDTPs may cause increased friction, leading to extra power loss.
• WO-A-02/24843 describes a method of operating a camless internal combustion engine which comprises:
• EP-A-1338643 describes reduced phosphorus lubricating oil compositions for use as passenger car engine lubricants.
• compositions comprise a major amount of Group II-IV and ester base oils; an overbased calcium or magnesium salicylate detergent; an oil-soluble organo-molybdenum compound; an ashless dispersant; and a supplemental antioxidant.
• the supplemental antioxidant is said to reduce the tendency of base oils to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on metal surfaces and by viscosity growth.
• the supplemental antioxidant is to be present in an amount of from 0.1 to 5.0 wt %, the supplemental antioxidant is preferably present in an amount of 0.25 to 1.0 wt %.
• the Example in EP-A-1338643 employs supplemental antioxidant in an amount of 0.50% wt.
• U.S. Pat. No. 5,439,605 describes various low ash and light ash formulations for use as motor oils.
• the base oils present in the formulations may optionally contain antioxidant in an amount from about 0.5% to about 1.0%.
• the formulations are indicated to not contain phosphorus.
• EP-A-1338643 nor U.S. Pat. No. 5,439,605 are concerned with the development of phosphorus-free lubricating oils compositions for camless engines which have advantageous anti-wear properties, in particular giving reduced cylinder bore wear.
• lubricating oil compositions suitable for camless engines which exhibit advantageous anti-wear properties, in particular giving reduced cylinder bore wear. It is desirable to develop phosphorus-free lubricating oil compositions for camless engines which have beneficial anti-wear properties.
• the present invention provides a lubricating oil composition for internal combustion engines which composition is phosphorus-free and which composition comprises at least 60% wt. of base oil, wherein said base oil is selected from Group I, Group II, Group III and Group IV base oils or mixtures thereof, and at least 1.4% wt. of one or more antioxidants selected from the group of aminic antioxidants and/or phenolic antioxidants, based on the total weight of the lubricating oil composition.
• phosphorus-free in the present invention, is meant that the lubricating oil composition does not comprise any phosphorus-containing compounds therein.
• said one or more antioxidants are present in an amount of at least 1.6% wt., more preferably in an amount of at least 1.7% wt., based on the total weight of the lubricating oil composition.
• the lubricating oil composition of the present invention may comprise one or more aminic antioxidants.
• aminic antioxidants which may be conveniently used include alkylated diphenylamines, phenyl- ⁇ -naphthylamines, phenyl- ⁇ -naphthylamines and alkylated ⁇ -naphthylamines.
• Preferred aminic antioxidants include dialkyldiphenylamines such as p,p′-dioctyl-diphenylamine, p,p′-di- ⁇ -methylbenzyl-diphenylamine and N-p-butylphenyl-N-p′-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine, alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and n-t-dodecylphenyl-1-naphthylamine, 1-naphthylamine, arylnaph
• Preferred aminic antioxidants include those available under the following trade designations: “Sonoflex OD-3” (ex. Seiko Kagaku Co.), “Irganox L-57” (ex. Ciba Specialty Chemicals Co.) and phenothiazine (ex. Hodogaya Kagaku Co.).
• the lubricating oil composition of the present invention may comprise one or more phenolic antioxidants.
• phenolic antioxidants which may be conveniently used include C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid, 2-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-alkoxyphenols such as 2,6-di-t-butyl
• Preferred phenolic antioxidants include those available under the following trade designations: “Irganox L-135” (ex. Ciba Specialty Chemicals Co.), “Anteeji DBH” (ex. Kawaguchi Kagaku Co.,), “Yoshinox SS” (ex. Yoshitomi Seiyaku Co.), “Antage W-400” (ex. Kawaguchi Kagaku Co.), “Antage W-500” (ex. Kawaguchi Kagaku Co.), “Antage W-300” (ex. Kawaguchi Kagaku Co.), “Ionox 220AH” (ex. Shell Japan Co.), bisphenol A, produced by the Shell Japan Co., “Irganox L109” (ex.
• Ciba Speciality Chemicals Co. Ciba Speciality Chemicals Co.
• “Tominox 917” Ex. Yoshitomi Seiyaku Co.
• “Irganox L115” Ex. Ciba Speciality Chemicals Co.
• “Sumilizer GA80” ex. Sumitomo Kagaku
• “Antage RC” ex. Kawaguchi Kagaku Co.
• “Irganox L101” (ex. Ciba Speciality Chemicals Co.)
• Yoshinox 930 Ex. Yoshitomi Seiyaku Co.
• “Ionox 330” Ex. Shell Japan Co.).
• the amount of base oil incorporated in the lubricating oil composition of the present invention is preferably present in an amount of at least 60% wt., more preferably in an amount in the range of from 60 to 98% wt., most preferably in an amount in the range of from 75 to 90% wt., with respect to the total weight of the lubricating oil composition.
• Group I base oil base oil, “Group II” base oil, “Group III” base oil and “Group IV” base oil in the present invention are meant base oils according to the definitions of American Petroleum Institute (API) categories I, II, III and IV. Such API categories are defined in API Publication 1509, 15 th Edition, Appendix E, April 2002.
• API American Petroleum Institute
• Group I base oils contain less than 90% saturates (according to ASTM D2007) and/or greater than 0.03% sulphur (according to ASTM D2622, D4294, D4927 or D3120) and have a viscosity index of greater than or equal to 80 and less than 120 (according to ASTM D2270).
• Group II base oils contain greater than or equal to 90% saturates and less than or equal to 0.03% sulphur and have a viscosity index of greater than or equal to 80 and less than 120, according to the aforementioned ASTM methods.
• Group III base oils contain greater than or equal to 90% saturates and less than or equal to 0.03% sulphur and have a viscosity index of greater than 120, according to the afore-mentioned ASTM methods.
• Group IV base oils are polyalphaolefins (PAO).
• Group I to IV base oils used in the present invention, and various conventional known Group I to IV base oils selected from mineral oils and synthetic lubricating oils may be conveniently used.
• Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
• Naphthenic base oils have low viscosity index (VI) (generally 40-80) and a low pour point.
• Such base oils are produced from feedstocks rich in naphthenes and low in wax content and are used mainly for lubricants in which colour and colour stability are important, and VI and oxidation stability are of secondary importance.
• Paraffinic base oils have higher VI (generally >95) and a high pour point. Such base oils are produced from feedstocks rich in paraffins, and are used for lubricants in which VI and oxidation stability are important.
• Fischer-Tropsch derived base oils may be used as the base oil in the lubricating oil composition of the present invention, for example, the Fischer-Tropsch derived base oils disclosed in EP-A-776959, EP-A-668342, WO-A-97/21788, WO-00/15736, WO-00/14188, WO-00/14187, WO-00/14183, WO-00/14179, WO-00/08115, WO-99/41332, EP-1029029, WO-01/18156 and WO-01/57166.
• the Fischer-Tropsch derived base oils disclosed in EP-A-776959, EP-A-668342, WO-A-97/21788, WO-00/15736, WO-00/14188, WO-00/14187, WO-00/14183, WO-00/14179, WO-00/08115, WO-99/41332, EP-1029029, WO-01/18156 and WO-01/57
• Synthetic processes enable molecules to be built from simpler substances or to have their structures modified to give the precise properties required.
• Synthetic lubricating oils include hydrocarbon oils such as olefin oligomers (PAOs) (Group IV base oils) and dewaxed waxy raffinate.
• hydrocarbon oils such as olefin oligomers (PAOs) (Group IV base oils) and dewaxed waxy raffinate.
• Synthetic Group III hydrocarbon base oils sold by the Royal Dutch/Shell Group of Companies under the designation “XHVI” (trade mark) may be used.
• the base oil used in the present invention is constituted from mineral oils and/or synthetic base oils which contain more than 80% wt of saturates, preferably more than 90% wt., as measured according to ASTM D2007.
• the base oil used in the present invention contains less than 1.0% wt., preferably less than 0.1% wt. of sulphur, calculated as elemental sulphur and measured according to ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120.
• the viscosity index of base oil used in the present invention is more than 80, more preferably more than 120, as measured according to ASTM D2270.
• the base oil used in the present invention has a kinematic viscosity in the range of from 2 to 80 mm 2 /s at 100° C., more preferably of from 3 to 70 mm 2 /s, most preferably of from 4 to 50 mm 2 /s.
• the lubricating oil composition of the present invention preferably has a sulphated ash content of not greater than 1.3 wt. %, more preferably not greater than 1.1 wt. % and most preferably not greater than 1.0 wt. %, based on the total weight of the lubricating oil composition.
• the lubricating oil composition of the present invention preferably has a sulphur content of not greater than 1.2 wt. %, more preferably not greater than 0.8 wt. % and most preferably not greater than 0.05 wt. %, based on the total weight of the lubricating oil composition.
• the lubricating oil composition of the present invention may further comprise additional additives such as anti-wear additives, detergents, dispersants, friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal fix or seal compatibility agents, provided that said additive components do not contain any phosphorus therein.
• additional additives such as anti-wear additives, detergents, dispersants, friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal fix or seal compatibility agents, provided that said additive components do not contain any phosphorus therein.
• Suitable phosphorus-free anti-wear additives include boron-containing compounds such as borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali or alkaline earth metal) borates and borated overbased metal salts.
• the boron-containing anti-wear additives may be added to the lubricating oil composition of the present invention in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
• Typical detergents that may be used in the lubricating oil of the present invention include one or more salicylate and/or phenate and/or sulphonate detergents.
• metal organic and inorganic base salts which are used as detergents can contribute to the sulphated ash content of a lubricating composition, in a preferred embodiment of the present invention, the amounts of such additives are minimised.
• the salicylate and/or phenate and/or sulphonate detergents may be added in an amount in the range of from 0.01 to 20.0 wt. %, more preferably from 0.10 to 10.0 wt. %, based on the total weight of lubricating oil composition.
• salicylate detergents are preferred.
• the lubricating oil composition of the present invention may contain one or more salicylate detergents.
• the salicylate and/or phenate and/or sulphonate detergents independently, have a TBN (total base number) in the range of from 10 to 500 mg.KOH/g, more preferably in the range of from 30 to 350 mg.KOH/g and most preferably in the range of from 50 to 300 mg.KOH/g, as measured by ASTM D2894.
• TBN total base number
• the lubricating oil compositions of the present invention may additionally contain an ash-free dispersant which is preferably admixed in an amount in the range of from 5 to 15% wt., based on the total weight of the lubricating oil composition.
• Typical dispersants that may be conveniently employed in the lubricating oil composition of the present invention, include ash-free alkenyl- or alkyl-succinimides and polyalkenyl succininic acid esters or derivatives thereof. Such ash-free dispersants may be borated.
• the dispersants may have a high molecular weight (for example, of greater than 2000) or a low molecular weight (for example, of less than 2000, preferably less than 1200).
• Dispersants that may be employed in the lubricating oil composition of the present invention include those described in EP-A-1167497 and Japanese Patent Nos. 1367796, 1667140, 1302811 and 1743435.
• Preferred friction modifiers that may be used include fatty acid amides, more preferably unsaturated fatty acid amides.
• the total amount of unsaturated fatty acid amide compound added is preferably from 0.05 to 0.35% wt., based on the total weight of the lubricating oil composition.
• viscosity index improvers which may be used in the lubricating oil composition of the present invention include the styrene-butadiene copolymers, styrene-isoprene stellate copolymers and the polymethacrylate-based and ethylene-propylene copolymers and the like disclosed in Japanese Patent Nos. 954077, 1031507, 1468752, 1764494 and 1751082. Such viscosity index improvers may be conveniently employed in an amount in the range of from 1 to 20% wt., based on the total weight of the lubricating oil composition. Similarly, dispersing-type viscosity index improvers comprising copolymerized polar monomer containing nitrogen atoms and oxygen atoms in the molecule may also be used therein.
• Polymethacrylates such as, for example, those as disclosed in Japanese Patent Nos. 1195542 and 1264056 may be employed in the lubricating oil compositions of the present invention as effective pour point depressants.
• compounds such as alkenyl succinic acid or ester moieties thereof, benzotriazole-based compounds and thiodiazole-based compounds may be used in the lubricating oil composition of the present invention as corrosion inhibitors.
• Compounds such as, for example, dimethyl polycyclohexane, polyacrylate may be used in the lubricating oil composition of the present invention as defoaming agents.
• seal fix or seal compatibility agents include, for example, commercially available aromatic esters.
• the lubricating oil compositions of the present invention may be prepared by admixing the antioxidants selected from the group of aminic antioxidants and/or phenolic antioxidants, and, optionally, one or more further additives that are usually present in lubricating oils, for example as herein before described, with a mineral and/or synthetic base oil.
• Lubricating oil compositions of the present invention display reduced wear, in particular reduced cylinder bore wear. Accordingly, in a further embodiment of the present invention, there is provided the use of a lubricating oil composition as hereinbefore described to reduce wear, preferably cylinder bore wear, in an internal combustion engine, in particular in a camless internal combustion engine.
• a method of lubricating an internal combustion engine comprising applying a lubricating oil composition as hereinbefore described thereto.
• Tables 1 and 2 indicate the formulations that were tested.
• the aminic antioxidant used was that available under the trade designation “Irganox L-57” ex. Ciba Specialty Chemicals Co. (p,p′-dioctyl-diphenylamine).
• the phenolic antioxidant used was that available under the trade designation “Irganox L-135” ex. Ciba Speciality Chemicals Co. (octyl 3-(3,5-di-t-butyl-4-hydroxylphenyl)propionate).
• Table 3 indicates the physical characteristics of the formulations that were tested. TABLE 1 Comparative Comparative Additive Example 1 Example 2 Example 1 Example 2 Antifoam 30 ppm 30 ppm 30 ppm 30 ppm Magnesium/Calcium 3.85 3.85 3.85 3.85 3.85 Detergents (% wt.) Succinimide 7.5 7.5 7.5 7.5 Ashless Dispersant (% wt.) Aminic Antioxidant 1.7 1.7 0.3 0.3 (% wt.) Zinc — — 1.0 — dithiophosphate (% wt.) Pour point 0.2 0.2 0.2 0.2 depressant (% wt.) Viscosity index 18.5 11 18.5 18.5 modifier concentrate (A) (1) (% wt.) Base Oil HVI-105 (2) 5 — 5 5 (% wt.) HVI-65 (3) 53.25 19.75 53.65 54.65 (% wt.) XHVI-5.2 (4) 10 56 10 10 (% wt.
• Example 2 Example 3
• Example 4 Example 1
• Example 2 Vk*, 100° C. (cSt) 14.74 10.24 11.90 11.67 14.44 14.46 Vk*, 40° C. (cSt) 98.07 58.01 66.93 70.87 94.99 94.37 CCS**, ⁇ 25° C. 7730 6269 @ ⁇ 30° C. 6237 @ ⁇ 30° C. 5959 7304 6995 (mPa ⁇ s) (ASTM D5293) Mg (% wt.
• the oil system for the valve train was separated form the rest of the internal combustion engine, thereby allowing the lower part of the internal combustion engine to be lubricated with a “camless” type lubricant as it did not come into contact with the cam-follower area.
• a screening rig test was developed by Shell Global Solutions (UK) using a BMW Megane 1.6 litre gasoline engine.
• the test cycle mimicked short distance stop-start driving, in a similar manner to the ASTM Sequence V test.
• the Renault Megane 1.6 litre gasoline engine was modified to separate the oil supply and return to the overhead camshaft valve train in the cylinder head from their normal routes in and out of the cylinder block.
• the cylinder head was lubricated by a separate external electric pump in a circuit with reservoir and temperature control. A conventional fully-formulated lubricant was used in this circuit.
• test oil was used in the remainder of the original engine circuit below the head. The modifications were confined to the cylinder head, so that it could be re-used. It was possible to use the head for several test runs before it required overhauling. A new short motor was used for each test, which was stripped and measured beforehand, and the piston ring gaps were increased to give higher blow-by flow rate for increased severity.
• the standard test duration was 288 hours (12 days), running on a four hour cycle. The engine was stopped once a day for oil sampling and levelling/top-up.
• the engine used for the second series of tests was a Ford Zetec SE 1.7 litre DOHC, as used in the Puma Coupe. It was modified in a similar manner to the Megane engine in order to simulate camless operation. The rest of the test installation and method was the same as for the Megane test, except that all the tests were run to a duration of 576 hours (24 days).
• the screening rig testing is a publicly available commercial testing service that is available ex.
• Shell Global Solutions UK
• Cheshire Innovation Park P.O. Box 1, Chester CH1 3SH, UK.
• Example 1 it is apparent from Example 1 that the addition of a greatly increased amount of antioxidant not only reduces the bore wear step depth to levels below those observed in Comparative Example 2, but said increased amount of antioxidant also surprisingly reduces the thrust side bore wear step depth to levels below that observed in the ZnDTP-containing formulation of Comparative Example 1.
• Example 1 The formulations of Examples 1 and 2 were also tested under an extended test duration of 576 hours. The results for the extended testing are given in Table 5 below. TABLE 5 Average Thrust Side Bore Wear Step Depth at top ring reversal ( ⁇ m) Example 1* 5.85 Example 2* 20.85 Comparative Example 1** 2.6 Comparative Example 2** 9.7 *576 hours test duration **288 hours test duration
• test operational details for this rig were the same as those used with the Megane engine, except that all tests were run to the double duration (576 hours).
• the wear step measurement technique was slightly different, in that the total cross-sectional area of the material removed in the wear step was measured, rather than the maximum depth of the step.
• Example 2 exhibits advantageous anti-wear properties.
• Table 6 indicates the total cross-sectional area of material removed in the wear step of a screening rig using Ford Zetec SE 1.7 litre DOHC engine using the formulation of Example 2.
• Example 3 and 4 which comprised phenolic antioxidant rather than aminic antioxidant had even lower bore wear than the formulation of Example 2.

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