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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
• • 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
  • C10M169/06—Mixtures of thickeners 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
  • 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
  • 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
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
  • C10M2205/17—Fisher Tropsch reaction products
  • C10M2205/173—Fisher Tropsch reaction products 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
  • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
  • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
• • 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
  • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
• • 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
  • 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
  • C10M2215/10—Amides of carbonic or haloformic acids
  • C10M2215/102—Ureas; Semicarbazides; Allophanates
  • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
• • 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
  • C10N2030/06—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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/02—Bearings
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy

Definitions

• the present invention relates to a grease
• lubricating oils or greases are mostly employed therein with, in particular, very many machines utilizing a grease lubrication system where the sealing structure can be simplified and equipment made small and compact.
• the range of use is extremely broad, encompassing, for example, the various kinds of ball-and-roller bearings and sliding bearings which support rotating bodies, and also the sliding parts of ball joints and links or chains, gear wheels, wires and booms of cranes, etc., and the quality demanded of these rises year by year, with the prolongation of machine life and maintenance-free operation being problems common to all machinery.
• the cases where the lubricating performance of a grease in the rotating components or sliding parts of a machine falls, and the machine life runs out may be broadly divided into two. Firstly, there is the case where the grease is subject to oxidation when used at high temperature, so that there is solidification of the grease due to evaporation of the oil component or thermal polymerization, or the grease structure breaks down along with the formation of organic acids or
• Measures for overcoming the situation described in the first case above include methods aimed at extending the machine life by effectively incorporating a suitable antioxidant into the grease (see Japanese Patent
• Measures for overcoming the situation described in the second case above include methods where the grease base oil viscosity is raised and polymer or other viscosity enhancing agent incorporated, so that the lubricating film is thickened and metal/metal contact suppressed (see JP-A-2008 ⁇ 69282 ) , and methods where an antiwear agent, an extreme pressure agent, a solid lubricant or other load-resisting additive is
• the present invention addresses the problem of providing a grease composition with high wear resistance. As a result of painstaking research against this
• the present invention provides a grease composition which is characterized in that, in a grease composition containing a base oil and a thickener, there is employed, as an additive, a poly (meth) acrylate
• the grease composition relating to the present invention displays the effect of higher wear resistance when compared to conventional grease compositions.
• the grease composition of this embodiment contains, as indispensable constituent components, "base oil”, “thickener” and “additive”. Below, the individual
• the base oil employed in the grease composition of this mode of the invention is not particularly- restricted.
• the base oils belonging to Group I, Group II, Group III and Group IV, etc., of the API (American Petroleum Institute) base oil categories can be used on their own or in the form of mixtures.
• the Group I base oils include paraffinic mineral oils obtained by, for example, applying a suitable combination of purification means such as solvent
• Group II base oils include paraffinic mineral oils obtained by, for example,
• Group III base oils and Group 11+ base oils include, for example, the paraffinic mineral oils produced by
• synthetic oils include polyolefins, the diesters of dibasic acids like dioctyl sebacate, polyol esters, alkylbenzenes, alkylnaphthalenes, esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyl diphenyl ethers, fluorine-containing compounds
• olefin polymer and also their hydrogenated products. Any olefin may be used, and examples are ethylene, propylene, butene, and cx-olefins with five or more carbon atoms. In the production of the polyolefin, a single type of aforesaid olefin may be used on its own, or a combination of two or more types may be employed. In particular, from the point of view of enhancing the low temperature fluidity and the low temperature lubricity, the polyolefins referred to as poly- -olefin (PAO) synthetic oils are preferred, and these are Group IV base oils.
• PAO poly- -olefin
• oils obtained by a GTL (gas to liquid) process which are oils synthesized from natural gas in a liquid fuel conversion technique employing the Fischer Tropsch method, have an extremely low sulphur component and aromatic component content when compared to the mineral oil base oils obtained by the refining of crude oil, and the paraffin structure proportion is extremely high, with the result that they have outstanding oxidation stability and an extremely low evaporation loss, so these can be favourably employed as the base oil in the present mode of the invention.
• the thickener used as an indispensable component in this mode of the invention is not particularly limited
• thickeners metal soaps, complex soaps, organified bentonite and silica, etc.
• urea-based thickeners are aliphatic diureas, alicyclic diureas, aromatic diureas, triureas, tetraureas and urea- urethanes.
• metal soaps are lithium 12- hydroxystearate, lithium stearate, calcium 12- hydroxystearate, calcium stearate, lithium complex, calcium complex, barium complex, aluminium complex, lithium-calcium mixed soaps and the like.
• organified bentonite is montmorillonite which has been treated with a quaternary ammonium salt
• silica is ultrafine silica powder produced by gas phase reaction, or this ultrafine silica powder after surface treatment with a lower alcohol such as methanol.
• Other examples include sulphonate complex,
• the preferred thickeners are the urea compounds formed by the reaction between an isocyanate and primary amine.
• the urea compound may be, for example, a diurea, triurea, tetraurea, pentaurea or a hexaurea, and it may be an aliphatic urea, an alicyclic urea or an aromatic urea, and it may also have other groups (like a urethane group) (as in the case of a urea-urethane) .
• a diurea thickener for example, is obtained by the reaction between 1 mol of diisocyanate and 2 mol of primary monoamine. Furthermore, a tetraurea thickener is obtained, for example, by the reaction between 2 mol of diisocyanate and 1 mol of primary diamine plus 2 mol of primary monoamine. Moreover, a triurea-monoureathane thickener is obtained, for example, by the reaction between 2 mol of diisocyanate and 1 mol of primary diamine plus 1 mol of primary monoamine and 1 mol of monoalcohol. Below, examples are given of the various starting materials employed when synthesizing these urea compounds .
• diisocyanate there are aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, etc. More specific examples are 4,4'- diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI) , naphthalene diisocyanate, p-phenylene
• the primary monoamine may be an aliphatic, alicyclic or aromatic monoamine.
• aliphatic amine there can be used a Cg to C24 saturated or unsaturated aliphatic amine, which may be branched or straight-chain, but straight-chain aliphatic amines are preferred.
• Specific examples of the primary monoamine include octylamine, decylamine, dodecylamine, tetradecylamine,
• the primary diamine may be an aliphatic, alicyclic or aromatic diamine.
• Examples include C 2 to C 12 diamines such as aliphatic diamines like ethylenediamine,
• trimethylenediamine tetramethylenediamine
• decamethylene-diamine alicyclic diamines such as diaminocyclohexane, and aromatic diamines such as phenylenediamine, benzidene, diaminostilbene and
• the monoalcohol may be an aliphatic, alicyclic or aromatic alcohol.
• aliphatic monoalcohol there can be used a Cs to C 23 ⁇ 4 saturated or unsaturated aliphatic alcohol, which may be branched or straight- chain, but straight-chain alcohols are preferred.
• octyl alcohol decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and oleyl alcohol
• an example of an alicyclic alcohol is cyclohexyl alcohol
• examples of the aromatic alcohols are benzyl alcohol, salicyl alcohol, phenethyl alcohol, cinnamyl alcohol,
• hydrocinnamyl alcohol and the like.
• alkyl diureas are preferred, more preferably the compounds represented by general formula (I) : R ⁇ NHCONH-R ⁇ NHCONH-R 3 (1 ⁇
• R 1 and R 3 each represents a Cs ⁇ i2 aliphatic
• R 2 represents a C 6 casuali 5 divalent aromatic group
• R 1 and R 3 are mutually independently an eight-carbon octyl group or a twelve-carbon lauryl group.
• R 2 is preferably the diphenylmethane group. In more preferred embodiments, there are used the compounds where R 2 is the
• the main thickener which is, for example, an aforesaid urea compound (such as an alkyl diurea) ⁇ .
• a urea compound such as an alkyl diurea
• tribasic calcium phosphate an alkali metal soap, an alkali metal complex soap, an alkaline earth metal soap, an alkaline earth complex soap, an alkali metal sulphonate, an alkaline earth metal sulphonate, other metal soaps, a metal terephthalamate salt, clay, a silica aerogel or other type of silica (silicon oxide) , or a fluoropolymer such as
• polytetrafluoroethylene, etc. and one of these can be used on its own or two or more can be used in combination. As well as these, it is also possible to employ any material which can confer a viscosity raising effect .
• the additive employed as an indispensable component in this embodiment is a poly (meth) acrylate which contains hydroxyl groups.
• This poly (meth) acrylate containing hydroxyl groups is a copolymer, and comprises a copolymer based on an alkyl (meth) acrylate having a Ci_2o alkyl group, and a hydroxyl-group-containing vinyl monomer, as the indispensable constituent monomers thereof.
• al) alkyl (meth) acrylates with a C1-4 alkyl group examples of which are methyl (meth) acrylate, ethyl (meth) acrylate, n- or iso ⁇ propyl (meth) acrylate, and n-, iso- or sec-butyl (meth) acrylate,
• alkyl (meth) acrylates with a Cs-ao alkyl group examples of which are n-octyl (meth) acrylate, 2- ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n- isodecyl (meth) acrylate, n-undecyl (meth) acrylate, n- dodecyl (meth) acrylate, 2-methylundecyl (meth) acrylate, n-tridecyl (meth) acrylate, 2-methyldodecyl
• (a3) alkyl (meth) acrylates with a C 5 - 7 alkyl group examples of which are n-pentyl (meth) acrylate and n- hexyl (meth) acrylate, etc.
• the monomers belonging to (al) and (a2) are preferred, with those belonging to (a2) further preferred.
• thos with 10 to 20 carbons in the alkyl group are preferred and those with 12 to 14 carbons are further preferred.
• the aforesaid hydroxyl-group-containing vinyl monomer (b) from which the copolymer is composed along with the alkyl (meth) acrylate having a Cl-20 alkyl group is a vinyl monomer containing one or more (preferably 1 or 2) hydroxyl groups in the molecule. Specific examples are
• hydroxyalkyl (Ci- 6 ) alkenyl (C3-10) ethers such as 2-hydroxyethyl propenyl ether, etc.
• hydroxyl-group-containing aromatic monomers such as o- r m- or p-hydroxystyrene, etc.
• polyhydric alcohols from tri- to octa-hydric: such as alkane polyols, as well as their
• sugar e.g. glycerol, pentaerythritol, sorbitol,
• (c2-l) vinyl monomers containing a primary amino group such as C3-6 alkenylamines [ (meth) allylamine, crotylamine, etc.], aminoalkyl (C 2 _e) (meth) acrylates
• (c2-3) vinyl monomers containing a tertiary amino group such as dialkyl (C ⁇ ) -aminoalkyl (C 2 -6)
• (meth) acrylates [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.], dialkyl (Ci_
• aminoalkyl (C 2 -e) (meth) acrylamides [dimethylaminoethyl - (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl- (meth) acrylamide, etc.], aromatic vinyl monomers containing a tertiary amino group [N,N- dimethylaminostyrene, etc.],
• (c4) monomers containing a nitrile group, such as (meth) acrylonitrile, and the like.
• a nitrile group such as (meth) acrylonitrile, and the like.
• other examples of such copolymerized monomers are aliphatic hydrocarbon-type vinyl monomers (d) . Examples of these are C2-20 alkenes [ethylene, propylene, butene, isobutylene, pentene, heptene,
• aromatic hydrocarbon-type vinyl monomers f ⁇ : examples of which are styrene, a- methylstyrene, vinyltoluene, 2, 4-dimethylstyrene, 4- ethylstyrene, 4-isopropylstyrene, 4 ⁇ butylstyrene, 4- phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, 4- crotylbenzene and 2-vinylnaphthalene, etc.
• vinyl esters, vinyl ethers and vinyl ketones examples of which are the vinyl esters of saturated C2-12 fatty acids [vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, etc.], Ci-12 alkyl, aryl or alkoxyalkyl vinyl ethers [methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl 2-methoxyethyl ether, vinyl 2-butoxyethyl ether, etc.] and Ci_ 3 alkyl or aryl vinyl ketones [methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc.].
• esters of unsaturated polycarboxylic acids (h) examples of which are the alkyl, cycloalkyl and aralkyl esters of unsaturated polycarboxylic acids, in particular the Cis alkyl di- esters of unsaturated dicarboxylic acids [such as maleic acid, fumaric acid and itaconic acid] [like dimethyl maleate, dimethyl fumarate, diethyl maleate and dioctyl maleate, etc . ] .
• vinyl monomers which contain a polyoxyalkylene chain (but not containing hydroxyl groups) (i) : examples of these being the mono- (meth) acrylates of a mono-alkyl (Ci-is) ether of a
• polyoxyalkylene glycol (C 2 ⁇ 4 alkylene group; degree of polymerization 2-50 ⁇ or of a polyoxyalkylene polyol
• carboxyl group-containing vinyl monomers (j) examples of which are vinyl monomers containing a single carboxyl group like unsaturated monocarboxylic acids [ (meth) acrylic acid, dimethyl ⁇ meth) acrylic acid, crotonic acid, cinnamic acid, etc.] and the monoalkyl (Ci- 8 ) esters of unsaturated dicarboxylic acids [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, etc.]; and vinyl monomers containing two or more carboxyl groups like maleic acid, fumaric acid, itaconic acid and citraconic acid, etc.
• the monomers (c) are preferred, and two or more of these monomers (c) may be used in combination.
• the monomers (c2) are preferred, with dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate further preferred.
• the hydroxyl value (hydroxyl group value) of the poly (meth) acrylate containing hydroxyl groups used as the additive lies between 10 and 100, preferably between 20 and 50 , and more preferably between 25 and 35.
• the hydroxyl value is a numerical value obtained by
• the grease composition of this mode of the invention may also optionally contain further additives such as antioxidants, rust inhibitors, oiliness agents, extreme pressure agents, anti-wear agents, solid lubricants, metal deactivators, polymers, metal-based cleaning agents, non metal-based cleaning agents, colouring agents, and the like.
• antioxidants include 2, 6-di- tert-butyl-4-methylphenol, 2,6-di-tert- butyl-p-cresol, p, p' -dioctyldiphenyl-iamine, N-phenyl-a- naphthylamine and phenothiazine .
• rust inhibitors include oxidized paraffin, carboxylic acid metal salts, sulphonic acid metal salts, carboxylic acid esters, sulphonic acid esters, salicylic acid esters, succinic acid esters, sorbitan esters and various kinds of amine salts.
• oiliness agents, extreme pressure agents and anti-wear agents include zinc dialkyldithiophosphate sulphide, zinc
• diallyldithiocarbamate sulphide diallyldithiocarbamate sulphide, organomolybdenum complexes, olefin sulphide, triphenyl phosphate,
• triphenyl-phosphorothionate triphenyl-phosphorothionate, tricresyl phosphate and other phosphate esters, and sulphurized oil/fats, etc.
• solid lubricants examples include molybdenum disulphide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene) , tungsten disulphide, graphite fluoride and calcium phosphate.
• metal deactivators include ⁇ , ⁇ 'TMdisalicylidene-l, 2- diaminopropane, benzotriazole, benzimidazole,
• polymers include polybutene, polyisobutene, polyisobutylene, polyisoprene, polymethacrylate, and the like.
• metal-based cleaning agents are metal sulphonates, metal salicylates and metal phenates.
• non metal-based cleaning agents include succinimides and the like. However, these examples are not intended to restrict the invention.
• the blended amount of base oil is preferably from 60-95 mass%, more preferably 70-90 mass% and still more preferably 75-90 massl, taking the total grease
• composition as 100 mass%.
• the amount of thickener ⁇ such as a urea compound
• poly (meth) acrylate incorporated is preferably from 2-20 mass% and more preferably 4-10 massl, taking the total grease composition as 100 mass%.
• the amount of the other additives is, for example, from 0.03 to 20 mass% by total of these optional additives
• a particularly preferred blending embodiment (in particular in regard to the thickener and the PMA
• the grease composition of this mode of the invention can be produced by generally-used grease production methods and is not particularly restricted but, as an example of the method for producing a urea grease
• a diurea thickener obtained by the reaction of 1 mol of diisocyanate and 2 mol of primary monoamine as the starting materials for the urea thickener or a tetraurea grease thickener obtained by the reaction of 2 mol of diisocyanate and 1 mol of primary diamine plus 2 mol of primary monoamine as the starting materials for the urea thickener, or a triurea-monoureathane obtained by the reaction of 2 mol of diisocyanate, 1 mol of primary diamine, 1 mol of primary monoamine plus 1 mol of mono-alcohol as the starting materials for the urea thickener, is synthesized along with the base oil in each case in a grease production kettle, to produce the grease used.
• a more specific production method having carried out the synthesis reaction of the
• the temperature is raised to a temperature of about 180°C, after which cooling is performed and, at a temperature of 100-80°C, the additive ⁇ the. hydroxyl-group-containing
• poly (meth) acrylate derivative ⁇ is incorporated and thorough mixing performed, following which the mixture is cooled to room temperature. Thereafter, a homogenous grease composition can be obtained using a kneading machine (such as a triple roll mill or the like ⁇ .
• the dropping point of the grease composition in this mode of the invention is preferably at least 180°C, more preferably at least 210°C, still more preferably at least 250°C and in particular over or above 260°C. If the dropping point of the grease composition is at least 180°C, it is thought that the possibility of lubrication problems arising such as, for example, loss in viscosity at high temperature and accompanying leakage or seizing, etc., is suppressed.
• the dropping point refers to the temperature at which there is breakdown of the thickener structure in the case of a grease possessing viscosity, when the temperature is raised. Measurement of the dropping point can be carried out in accordance with JIS K2220 8.
• the consistency of the grease in this mode of the invention preferably lies between grade 000 and grade 6 (85-475), more preferably between grade 0 and grade 4 (175-385), and still more preferably between grade 1 and grade 3 (220-340) .
• the consistency denotes the physical hardness of the grease.
• measurement of the worked penetration may be carried out in accordance with JIS 2220 7.
• Friction testing was carried out based on the high speed four ball wear test in ASTM D2596, using steel ball bearings under conditions comprising a rotation rate of 1200 rpm, a load of 40 kgf and ambient temperature (no temperature control) for 30 minutes, and then evaluation conducted from the wear-scar diameter on the stationary balls .
• EPS EPS
• braking equipment ball joints, door hinges, handles, the cooling fan motor, brake expanders and various other types of components, etc.
• the cooling fan motor brake expanders and various other types of components, etc.
• it is suitable for the various lubricated regions of power shovels, bulldozers, cranes and other types of
• the starting materials employed in the working examples and comparative examples were as follows.
• thickeners A and B diurea components with the following chemical structures were employed as thickeners .
• Thickener A urea type I
• Thickener C urea type III
• R 2 is the diphenylmethane group and Ri is the eight-carbon octyl group, R 3 is the twelve- carbon lauryl group and R 4 is the six-carbon phenyl group.
• Thickener D This was a commercially-availabl ⁇ lithium 12-hydroxystearate for industrial use.
• Base oil A This is a paraffinic mineral oil
• Base oil B This is a poly-a-olefin (PAO) synthetic oil belonging to Group IV, and it comprises a mixture of a low viscosity PAO and a high viscosity PAO so as to adjust the kinematic viscosity at 100°C to 15.4 mm 2 /s.
• the kinematic viscosity of the PAO mixture at 40°C is 118.9 mm 2 /s, and its viscosity index is 136.
• Base oil C This is an oil obtained by means of a GTL (gas to liquid) process, synthesized by the Fischer Tropsch method, and belongs to Group III; its kinematic viscosity is 8.2 mm 2 /s at 100°C and 47.9 mm 2 /s at 40 P C; and its viscosity index is 144.
• Additive B Hydroxyl-group-free PMA ⁇ commercial name: Aclube V-815, produced by Sanyo Chemical Industries Ltd; Mw - 2.1 x 10 4 )
• Additive C Hydroxyl-group-free PMA (commercial name: Aclube 812, produced by Sanyo Chemical Industries
• Additive E Ethylene-a-olefin copolymer (commercial name: Lucant HCIOO, produced by Mitsui Chemicals Inc.)
• Additive F Polybutene (commercial name: Nisseki Polybutene HV-100, produced by the JX Nippon Oil & Energy Corp. )
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 1 obtained by the usual method for producing a urea grease.
• the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
• 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4 , 4 ' - diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• the octylamine and laurylamine were
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 2 obtained by the usual method for producing a urea grease.
• the mol ratio of the dxisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
• 60 wt% of the total amount of the previously-prepared synthetic oil, i.e. base oil B was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4 , 4' ⁇ dxisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• the octylamine was dissolved in the remaining 40 wt% of the synthetic oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type I thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly (meth) acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 2 was obtained using a triple roll mill.
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 3 obtained by the usual method for producing a urea grease.
• the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
• 60 wt% of the total amount of the previously-prepared Group III base oil, i.e. base oil C was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4, 4' - diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• the octylamine was dissolved in the remaining 40 wt% of the Group III base oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type I thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly (meth ) acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 3 was obtained using a triple roll mill.
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the greases according to Working Examples 4 to 6 respectively obtained by the usual method for producing a urea grease.
• thickeners used here was a ratio of 1 : 2.
• diphenylmethane-4, 4' -diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• the octylamine and laurylamine were respectively dissolved in the remaining 40 wt% of the Group I base oil and introduced, in turn, into the trial-production kettle, to bring about reaction and formation of the diurea type II thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 7 obtained by the usual method for producing a urea grease.
• the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
• 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4 , 4' - diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• the octylamine was dissolved in the remaining 40 wt% of the Group I base oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type I thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly (meth) acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 7 was obtained using a triple roll mill.
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 8 obtained by the usual method for producing a urea grease.
• the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
• the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4 , 4 ' ⁇ diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• the octylamine was mixed with the synthetic oil, i.e. base oil B, and the laurylamine was mixed and dissolved in base oil C belonging to Group III, and these introduced in turn into the trial-production kettle, to bring about reaction and formation of the diurea type II thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl- group-containing pol (meth) acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 8 was obtained using a triple roll mill.
• additive A that is to say the hydroxyl- group-containing pol (meth) acrylate derivative
• the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 9 obtained by the usual method for producing a urea grease.
• the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
• 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4, 4' - diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
• aniline was mixed and dissolved in the remaining 40 wt% of the Group I base oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type III thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing
• poly (meth) acrylate derivative was then added at this temperature of 80°C and, after thorough stirring and mixing, cooling continued down to room temperature.
• Comparative Example 1 was the base grease in which no additive was incorporated.
• Comparative Example 2 additive B was incorporated.
• Comparative Example 3 additive C was incorporated.

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