WO2011118814A1 - Grease composition - Google Patents
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- WO2011118814A1 WO2011118814A1 PCT/JP2011/057462 JP2011057462W WO2011118814A1 WO 2011118814 A1 WO2011118814 A1 WO 2011118814A1 JP 2011057462 W JP2011057462 W JP 2011057462W WO 2011118814 A1 WO2011118814 A1 WO 2011118814A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M169/02—Mixtures of base-materials and thickeners
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
- C10M2207/1236—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic used as thickening agent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/126—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 monocarboxylic
- C10M2207/1265—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 monocarboxylic used as thickening agent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- 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
- C10N2010/02—Groups 1 or 11
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 composition.
- the present invention relates to a grease composition used for a main bearing that receives a main shaft incorporated in a wind turbine generator and a pitch bearing that receives a blade shaft.
- a grease composition is used for lubrication of a bearing that receives a large load, such as a main bearing that receives a main shaft and a pitch bearing that receives a blade shaft incorporated in a wind power generator.
- a bearing that receives a large load such as a main bearing that receives a main shaft and a pitch bearing that receives a blade shaft incorporated in a wind power generator.
- Such main bearings and pitch bearings are constantly subject to fluctuations and minute fluctuations due to changes in wind speed and minute control of the blades, and are in an environment where fretting wear is likely to occur.
- Replacing a bearing in the event of a failure requires great effort and cost, and therefore a lubricant that has excellent fretting resistance and is unlikely to cause damage to the bearing over a long period of time is required.
- a grease composition based on an ester synthetic oil having a kinematic viscosity at 100 ° C. of 200 to 2500 mm 2 / s has been proposed (see Patent Document 1). Furthermore, a grease composition is disclosed that uses a high-viscosity base oil for a grease composition and, if necessary, contains an extreme pressure agent to improve durability against a large load (non-patent document). 1 and 2).
- examples of the grease composition used in the wind power generator include a composition containing a base oil, a thickener, and oleoyl sarcosine (see Patent Document 2), and a kinematic viscosity at 40 ° C. of 70 to 250 mm 2.
- a composition containing a base oil that is / s, a thickener, and a carboxylic acid-based anticorrosive additive has been proposed (see Patent Document 3).
- Main bearings and pitch bearings used in wind turbine generators are required to reduce not only fretting wear due to rotation of the main shaft and wing shaft, but also reduction of bearing wear due to receiving heavy spindles and wing shafts.
- it is difficult to simultaneously suppress bearing wear and fretting wear.
- a high-viscosity base oil is used, there is a problem that the low-temperature startability is deteriorated with respect to the low-viscosity base oil and fretting wear is increased.
- the present invention (1) A grease composition containing a base oil and a thickening agent, wherein the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a poly- ⁇ -olefin ( A grease composition containing component A), (2) The grease composition according to (1), wherein the kinematic viscosity of the component A at 40 ° C. is 600 mm 2 / s or more, (3) The grease composition according to (1) or (2), wherein the component A is contained in an amount of 20% by mass or more based on the total amount of the composition, (4) The grease composition according to any one of (1) to (3) above, wherein the base oil has a kinematic viscosity at 40 ° C.
- the base oil contains 10 to 70% by mass of a B component having a kinematic viscosity at 40 ° C. of 70 mm 2 / s or less based on the total amount of the composition.
- a grease composition used for a wind power generator comprising: a main bearing connected to a main shaft to which a wing of the wind power generator is connected; and a pitch bearing connected to a wing shaft incorporated in the wing.
- the grease composition of the present invention bearing wear and fretting wear under a high load can be simultaneously suppressed, and the life of the bearing can be extended. Further, according to the present invention, it is possible to provide a grease composition capable of suppressing fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swinging direction. A grease composition that is small and excellent in low-temperature characteristics can be provided.
- the grease composition of the present invention comprises a base oil and a thickener, and the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a poly- ⁇ -olefin (component A). ).
- the poly- ⁇ -olefin produced using a metallocene catalyst can suppress bearing wear and fretting wear at the same time, thereby prolonging the life of the bearing, particularly fretting caused by minute vibration in the swinging direction.
- those having a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more are used from the viewpoint of suppressing fretting wear associated with load fluctuations in the thrust direction.
- the kinematic viscosity at 40 ° C. of the component A is preferably 600 mm 2 / s or more, and more preferably 1000 mm 2 / s or more.
- the upper limit is not particularly limited, but is about 200,000 mm 2 / s from the viewpoint of keeping the viscosity of the base oil moderate.
- the kinematic viscosity at 100 ° C. is preferably 32 mm 2 / s or more, more preferably 90 mm 2 / s or more, from the same viewpoint as described above.
- Examples of the metallocene catalyst for obtaining the component A include a catalyst containing a combination of a metallocene compound and a promoter.
- a metallocene compound a compound represented by the general formula (I) (RC 5 H 4 ) 2 MX 2 (I)
- the metallocene compound represented by these is preferable.
- R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- M represents a transition metal element of Group 4 of the periodic table
- X represents a covalent bond or an ionic bond. Represents a ligand.
- R is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
- M include titanium, zirconium, and hafnium. Among these, zirconium is preferable.
- Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 to 20 carbon atoms.
- 1 to 12 phosphorus-containing hydrocarbon groups for example, diphenylphosphine group
- 1 to 20 carbon atoms preferably 1 to 12 silicon-containing hydrocarbon groups (for example, trimethylsilyl group)
- 1 to 20 carbon atoms are preferable Includes boron compounds containing 1 to 12 hydrocarbon groups or halogens (for example, B (C 6 H 5 ) 4 , BF 4, etc.).
- halogens for example, B (C 6 H 5 ) 4 , BF 4, etc.
- hydrogen atoms, halogen atoms, hydrocarbons A group selected from a group and an alkoxy group is preferred.
- metallocene compound represented by the general formula (I) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (Iso-propylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride , Bis (texylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylmethylcyclopentadienyl) zirco Um dichloride, bis (cyclopent
- methylaluminoxane is preferable.
- the methylaluminoxane is not particularly limited and conventionally known methylaluminoxane can be used.
- the general formula (II) or the general formula (III) can be used.
- p represents the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.
- the method for producing methylaluminoxane include a method in which methylaluminum and a condensing agent such as water are brought into contact with each other, but the means is not particularly limited and may be carried out according to a known method.
- the compounding ratio of the metallocene compound and methylaluminoxane is usually 15 to 150, preferably 20 to 120, more preferably 25 to 100 for the methylaluminoxane / metallocene compound (molar ratio). If it is 15 or more, catalytic activity is exhibited, and the yield of a trimer or more suitable as a base oil for a lubricating oil does not decrease due to the formation of an ⁇ -olefin dimer. On the other hand, if it is 150 or less, deashing removal of the catalyst will not be incomplete.
- metallocene catalysts other than those mentioned above include metallocene catalysts that use a metallocene compound having a crosslinking group.
- a metallocene compound having two crosslinking groups is preferable, and a metallocene compound having meso symmetry is particularly preferable.
- Examples of the metallocene catalyst using the metallocene compound having meso symmetry include, for example, (a) a metallocene compound represented by the following formula (IV), and (b) (b-1) a metallocene compound of the component (a) Alternatively, a metallocene catalyst containing at least one component selected from a compound capable of reacting with a derivative thereof to form an ionic complex and (b-2) aluminoxane may be mentioned.
- the compound represented by the formula (IV) is a mesosymmetric compound, and in the formula (IV), M represents a metal element belonging to Groups 3 to 10 of the periodic table.
- X represents a ⁇ -binding ligand, and when there are a plurality of X, a plurality of X may be the same or different, Y represents a Lewis base, and when there are a plurality of Y, a plurality of Y are the same or different It may be.
- A represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, — SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - and -AlR 1 - shows a bridging group selected from 2 in the formula (IV) Two A's may be the same or different.
- R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms.
- q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
- E is a group represented by the following formulas (V) and (VI), and two Es in the formula (IV) are the same.
- the mesosymmetric compound refers to a transition metal compound in which two bridging groups bridge two Es in a bonding mode of (1,1 ′) (2,2 ′).
- R 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, a silicon-containing group or a heteroatom-containing group. Represents a group selected from: When several R ⁇ 2 > exists, they may mutually be same or different.
- the bond indicated by the wavy line represents the bond with the bridging group A.
- crosslinking group A in the formula (IV) a group represented by the following formula (VII) is preferable.
- B in the formula (VII) is a skeleton of a bridging group and represents a carbon atom, a silicon atom, a boron atom, a nitrogen atom, a germanium atom, a phosphorus atom, or an aluminum atom.
- R 3 represents a hydrogen atom, a carbon atom, an oxygen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an amine-containing group, or a halogen-containing group.
- n is 1 or 2.
- metallocene compound represented by the formula (IV) include (1,1′-ethylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2 , 2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) (2 , 2′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1 , 1′-ethylene) (2,2′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2 2′-ethylene) -bis (5,6-dimethylin
- any compound can be used as long as it can react with the metallocene compound of the component (a) to form an ionic complex.
- Those represented by the following general formulas (VIII) and (IX) can be preferably used.
- L 1 represents a Lewis base
- L 2 represents M 2 , R 5 R 6 M 3 , R 7 3 C or R 8 M 3
- [Z] ⁇ represents a non-coordinating anion [Z 1 ] ⁇ or [Z 2 ] ⁇ .
- [Z 1 ] ⁇ is an anion in which a plurality of groups are bonded to the element, that is, [M 1 G 1 G 2 ...
- G f ] ⁇ (where M 1 is a group 5-15 element in the periodic table, Preferably, it represents a group 13 to 15 element of the periodic table, G 1 to G f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, or 1 to carbon atoms.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R 5 and R 6 are a cyclopentadienyl group and a substituted group, respectively.
- R 7 represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
- R 8 represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.
- M 2 includes elements in groups 1 to 3, 11 to 13, and 17 of the periodic table, and M 3 represents elements in groups 7 to 12 of the periodic table.
- L 1 examples include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.
- R 4 examples include hydrogen, methyl group, ethyl group, benzyl group, and trityl group.
- R 5 and R 6 include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
- R 7 examples include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R 8 include tetraphenylporphyrin, phthalocyanine, allyl, methallyl and the like. .
- M 2 include Li, Na, K, Ag, Cu, Br, I, and I 3.
- M 3 include Mn, Fe, Co, Ni, and Zn. And so on.
- [Z 1 ] ⁇ that is, [M 1 G 1 G 2 ... G f ]
- specific examples of M 1 include B, Al, Si, P, As, Sb, etc., preferably B and Al.
- G 1 and G 2 to G f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like.
- Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Romechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, di
- Noncoordinating anions i.e. pKa of -10 or less Bronsted acid alone or Bronsted acid and Lewis acid combined conjugate base [Z 2] -
- Examples of trifluoromethanesulfonic acid anion (CF 3 SO 3 ) ⁇ bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO 4 ) ⁇ , trifluoroacetate anion (CF 3 CO 2 ) ⁇ , Hexafluoroantimony anion (SbF 6 ) ⁇ , fluorosulfonic acid anion (FSO 3 ) ⁇ , chlorosulfonic acid anion (ClSO 3 ) ⁇ , fluorosulfonic acid anion / 5-antimony fluoride (FSO 3 / SbF 5 ) -
- an ionic compound that reacts with the metallocene compound (a) to form an ionic complex, ie, (b-1) component compound include tetrakis (pentafluorophenylboric acid) N, N -Dimethylanilinium, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (Tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methyl tetrakis
- R 9 represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, arylalkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen atom
- w represents an average degree of polymerization, Usually an integer of 2 to 50, preferably 2 to 40, wherein each R 9 may be the same or different, and a chain aluminoxane represented by the general formula (XI)
- Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
- the aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.
- the use ratio of (a) catalyst component to (b) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (b-1) compound is used as (b) catalyst component.
- the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer becomes high, which is not practical.
- the compound (b-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical.
- the catalyst component (b), (b-1) and (b-2) can be used alone or in combination of two or more.
- the catalyst in the present invention may contain the components (a) and (b) as main components, and (a) component, (b) component and (c) organoaluminum compound. May be contained as a main component.
- organoaluminum compound of component (c) the general formula (XII) (R 20 ) v AlQ 3-v (XII) (Wherein R 20 represents an alkyl group having 1 to 10 carbon atoms, Q represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms) Which is an integer).
- Specific examples of the compound represented by the general formula (XII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used singly or in combination of two or more.
- the use ratio of the component (a) to the component (c) is a molar ratio, preferably 1: 1 to 1: 10,000, more preferably 1: 5 to 1: 2,000, and still more preferably 1: 10 to 1: 1,000.
- the activity per transition metal can be improved.
- the amount is too large, the organoaluminum compound is wasted and a large amount remains in the ⁇ -olefin polymer, which is not preferable.
- an ⁇ -olefin having 3 to 14 carbon atoms is usually used.
- ⁇ -olefins selected from 1-octene, 1-decene, and 1-dodecene are preferred, and 1-decene is particularly preferred because an ⁇ -olefin having the desired kinematic viscosity is easily obtained.
- the A component may be a copolymer using two or more kinds of ⁇ -olefins having 3 to 14 carbon atoms, in which case an ⁇ -olefin selected from 1-octene, 1-decene and 1-dodecene is particularly preferred. preferable.
- the mixing ratio of the metallocene compound represented by the general formula (I) or (IV) and the ⁇ -olefin having 3 to 14 carbon atoms is usually 0.01 to 0. .4, preferably 0.05 to 0.3, and more preferably 0.1 to 0.2.
- 0.01 or more sufficient catalytic activity is obtained, and when 0.4 or less, the yield of the trimer or more oligomer suitable as the base oil of the lubricating oil is improved, and the catalyst is deashed. Removal will not be incomplete.
- the polymerization of the ⁇ -olefin having 3 to 14 carbon atoms is preferably performed in the presence of hydrogen.
- the amount of hydrogen added is usually 0.1 to 500 kPa, preferably 0.5 to 300 kPa, and more preferably 1 to 200 kPa.
- the amount of hydrogen added is 0.1 kPa or more, sufficient catalytic activity can be obtained.
- it is 500 kPa or less, the production of a saturated product of raw material ⁇ -olefin can be reduced, and the desired poly- ⁇ - The olefin yield is improved.
- the polymerization of the ⁇ -olefin having 3 to 14 carbon atoms is not limited in the reaction method, and may be performed in the absence of a solvent or in a solvent, and any method may be used.
- a reaction solvent for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane Halogenated hydrocarbons such as chloroform and dichloromethane.
- the temperature of the polymerization reaction is usually 0 to 200 ° C., preferably 20 to 180 ° C., more preferably 30 to 150 ° C. By being in the above range, sufficient catalytic activity can be obtained, and the yield of trimer or higher oligomer suitable as a base oil for lubricating oil can be improved. Polymerization by the above method can produce an A component having a selectivity of trimer or higher of 50% or higher.
- component A is different from conventional poly ⁇ -olefins in terms of molecular structure and high homogeneity, and exhibits high oxidation stability and high viscosity index, and is excellent as a lubricating base oil.
- the viscosity index of the component A is preferably from 150 to 350, more preferably from 165 to 300, from the viewpoint of increasing fluidity at low temperatures.
- the grease composition of the present invention has a high viscosity index, which, unlike conventional grease compositions using poly ⁇ -olefins, improves low-temperature viscosity characteristics and depends on a viscosity index improver. The degree goes down.
- the grease composition of the present invention can also suppress fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swing direction.
- the grease composition of the present invention preferably contains a B component having a kinematic viscosity at 40 ° C. of 70 mm 2 / s or less from the viewpoint of improving fretting wear and pumpability.
- the kinematic viscosity at 40 ° C. of the component B is preferably 10 to 50 mm 2 / s, more preferably 20 to 45 mm 2 / s, and still more preferably 20 to 40 mm 2 / s.
- the kinematic viscosity at 100 ° C. of the component B is preferably 13 mm 2 / s or less, more preferably 3 to 9 mm 2 / s.
- the viscosity index of the component B is preferably from 70 to 250, more preferably from 120 to 200, from the viewpoint of improving fluidity at low temperatures.
- Component B is, for example, an ⁇ -olefin (single or mixed) oligomer having 4 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, or an olefin such as a co-oligomer of 1-decene and ethylene. It is an oligomer, and each may be used alone or as a mixture. These olefin oligomers may be synthesized by a known production method, or may be synthesized by a production method as described in JP-A-07-133234 and JP-A-03-131612.
- any base oil such as a diester, polyol ester, aromatic ester, alkyl-substituted diphenyl ether, or mineral oil may be used, but a synthetic oil having a pour point of ⁇ 35 ° C. or lower is preferable from the viewpoint of low temperature fluidity.
- the base oil may further contain other synthetic oil or mineral oil, if necessary, in the A component and preferably the B component.
- Examples of other synthetic oils include, as aromatic oils, alkylbenzenes such as monoalkylbenzene and dialkylbenzene, and alkylnaphthalenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene.
- ester oils include dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, ditridecyl glutarate, and methyl acetyl cinnolate, or trioctyl trimellitate, Aromatic ester oils such as tridecyl trimellitate and tetraoctyl pyromellitate, and further trimethylolpropane caprylate, trimethylolpropane verargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol verargonate, etc.
- ether oils include polyglycols such as polyethylene glycol, polypropylene glycol, polyethylene glycol monoether, and polypropylene glycol monoether, or monoalkyl triphenyl ether, alkyl diphenyl ether, dialkyl diphenyl ether, pentaphenyl ether, tetraphenyl ether, monoalkyl tetra Examples thereof include phenyl ether oils such as phenyl ether and dialkyl tetraphenyl ether, olefinic oligomers such as normal paraffin, isoparaffin, polybutene, polyisobutylene, 1-decene oligomer, and 1-decene and ethylene co-oligomer.
- the above synthetic oils may be used alone or as a mixture.
- the mineral oil a refined product obtained by appropriately combining vacuum distillation, oil removal, solvent extraction, hydrocracking, solvent dewaxing, sulfuric acid washing, white clay purification, hydrorefining, and the like can be used.
- the base oil preferably has a kinematic viscosity at 40 ° C. of 150 to 2000 mm 2 / s, more preferably 200 to 1000 mm 2 / s, from the viewpoint of excellent fretting wear and bearing wear. More preferably, it is 300 to 700 mm 2 / s.
- the kinematic viscosity at 100 ° C. of the base oil is preferably 14 to 300 mm 2 / s, more preferably 16 to 150 mm 2 / s.
- the viscosity index of the base oil is preferably from 90 to 350, more preferably from 120 to 350, from the viewpoint of increasing fluidity at low temperatures.
- the grease composition of the present invention suppresses bearing wear and fretting wear at the same time, thereby prolonging the life of the bearing, and in addition to fretting wear due to minute vibrations in the swinging direction, in addition to load fluctuations in the thrust direction.
- the component A is preferably contained in an amount of 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, based on the total amount of the composition.
- the upper limit is not particularly limited, but is usually 90% by mass from the viewpoint of the blend ratio of the base oil.
- the content of component A in the base oil is preferably 35% by mass or more, more preferably 45 to 85% by mass, from the same viewpoint as described above.
- the base oil preferably contains 10 to 70% by mass of the component B with respect to the total amount of the composition because it is excellent in fretting wear and pumpability and can be easily adjusted to a high viscosity. Is 15 to 60% by mass, and more preferably 20 to 50% by mass.
- the content of the B component in the base oil is preferably 12 to 65% by mass, more preferably 12 to 60% by mass, and still more preferably 17 to 55% by mass, from the same viewpoint as described above. .
- the content ratio of the A component and the B component in the base oil is expressed as a mass ratio (A component / B component) from the viewpoint of ease of grease production and the appropriate viscosity of the base oil. It is preferably 0.45 to 9.0, and more preferably 1.0 to 5.0.
- the grease composition of the present invention contains a thickener.
- a thickener both organic and inorganic thickeners can be used, and a soap-based thickener is preferable from the viewpoint of wear resistance.
- Li soap, Li complex soap, Ca soap, Ca sulfonate complex soap, or Ca complex soap is more preferable.
- the fatty acid constituting the soap contains 12-hydroxystearate. It is a waste.
- soap contains Li, More preferably, it is Li complex soap.
- Li complex soap is excellent in performance balance from low temperature to high temperature.
- As the thickener urea compounds, bentonite, silica, carbon black, PTFE, etc. may be used. These may be used alone or in combination.
- the content of the thickener is not limited as long as grease can be formed and maintained with the above base oil, but in addition to fretting wear due to minute vibrations in the swing direction, fretting wear due to load fluctuations in the thrust direction. From the viewpoint of suppressing the amount and the excellent pumpability, it is preferably 17% by mass or less based on the total amount of the composition of the present invention. From the above viewpoint, the blending amount of the thickener is more preferably 14% by mass or less, and particularly preferably 12% by mass or less, based on the total amount of the composition.
- the content of the thickener is expressed as the amount of carboxylic acid constituting the thickener for the soap-type thickener.
- the urea-based thickener is expressed as a reaction amount of isocyanate and amine.
- Carboxylic acids include crude fatty acids obtained by hydrolyzing fats and oils to remove glycerol, monocarboxylic acids such as stearic acid, monohydroxycarboxylic acids such as 12-hydroxystearic acid, dibasic acids such as azelaic acid, terephthalic acid, Examples include aromatic carboxylic acids such as salicylic acid and benzoic acid. In addition, you may use ester of carboxylic acid. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the alkali include metal hydroxides such as alkali metals or alkaline earth metals. Examples of the metal include sodium, calcium, lithium, and aluminum.
- an extreme pressure agent containing sulfur is preferably blended in an amount of 0.01 to 10% by mass based on the total amount of the composition from the viewpoint of obtaining blending effects such as prevention of seizure.
- extreme pressure agents include zinc dialkyldithiophosphate (ZnDTP), molybdenum dialkyldithiophosphate (MoDTP), zinc dithiocarbamate (ZnDTC), molybdenum dithiocarbamate (MoDTC), dithiocarbamine (DTC), thiophosphate, sulfurized oil, Examples include dibenzyl disulfide and thiadiazole. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- the grease composition of the present invention may contain a resin / wax soluble in a base oil such as petroleum resin or polyethylene, and among them, a petroleum resin is preferable.
- the blending amount of the petroleum resin is preferably 0.5 to 35% by mass based on the total amount of the composition from the viewpoint of maintaining an appropriate viscosity and obtaining good low-temperature torque properties. From the above viewpoint, the blending amount of the petroleum resin is more preferably 1 to 30% by mass, and more preferably 2 to 25% by mass based on the total amount of the composition.
- a cyclopentadiene type is preferable, a product obtained by thermal copolymerization of a cyclopentadiene and an ⁇ -olefin or a monovinyl aromatic hydrocarbon, and a product obtained by hydrogenating these by a usual method as necessary. Or a mixture thereof.
- cyclopentadiene cyclopentadiene, a multimer thereof, an alkyl-substituted product thereof, or a mixture thereof can be used.
- Industrially, about 30 mass of cyclopentadiene obtained by steam cracking such as naphtha is used.
- a cyclopentadiene fraction containing at least%, preferably at least about 50% by weight.
- This CPD fraction may contain an olefin monomer copolymerizable with these alicyclic dienes.
- the olefinic monomer include aliphatic diolefins such as isoprene, piperylene and butadiene, and alicyclic olefins such as cyclopentene.
- concentration of these olefins is preferably low, but is acceptable if it is about 10% by mass or less per cyclopentadiene.
- ⁇ -olefins which are raw materials for copolymerization with cyclopentadiene
- ⁇ -olefins having 4 to 18 carbon atoms, preferably 4 to 12 carbon atoms, and mixtures thereof are used, among which ethylene, propylene or 1- A derivative from butene or the like, or a decomposition product of paraffin wax is preferably used. It is industrially preferred that the ⁇ -olefins be blended in less than about 4 moles per mole of cyclopentadiene.
- monovinyl aromatic hydrocarbons include styrene, o, m, p-vinyltoluene, ⁇ , ⁇ -methylstyrene, and the like. These monovinyl aromatic hydrocarbons may contain indenes such as indene, methylindene and ethylindene, and industrially, it is advantageous to use a so-called C9 fraction obtained by steam cracking such as naphtha. . When monovinyl aromatic hydrocarbons are used as a copolymerization raw material, it is industrially preferable to add less than about 3 moles per mole of cyclopentadiene.
- the grease composition of the present invention preferably has a blending degree of 220 to 350 from the viewpoint of adjusting the hardness of the grease to maintain good low temperature torque characteristics and preventing bearing wear and fretting wear. From the above viewpoint, the penetration is preferably 250 to 340, more preferably 265 to 320.
- an antioxidant in the grease composition of the present invention, an antioxidant, a rust preventive agent, a solid lubricant, a filler, an oily agent, a metal deactivator, if necessary, within the range where the object of the present invention is achieved.
- blend additives such as a water-resistant agent, another extreme pressure agent, an antiwear agent, a viscosity index improver, and a coloring agent.
- antioxidants examples include amine-based antioxidants such as alkylated diphenylamine, phenyl- ⁇ -naphthylamine, alkylated- ⁇ -naphthylamine, 2,6-di-t-butyl-4-methylphenol, 4,4 ′ -Phenolic antioxidants such as methylene bis (2,6-di-t-butylphenol), peroxide decomposition agents such as sulfur and ZnDTP, etc., and these are usually in the proportion of 0.05 to 10% by mass Used in.
- amine-based antioxidants such as alkylated diphenylamine, phenyl- ⁇ -naphthylamine, alkylated- ⁇ -naphthylamine, 2,6-di-t-butyl-4-methylphenol
- 4,4 ′ -Phenolic antioxidants such as methylene bis (2,6-di-t-butylphenol), peroxide decomposition agents such as sulfur and ZnDTP
- rust inhibitor examples include sodium nitrite, sulfonate, sorbitan monooleate, fatty acid soap, amine compound, succinic acid derivative, thiadiazole, benzotriazole, and benzotriazole derivative.
- Other extreme pressure agents and antiwear agents include, for example, phosphate ester, acid phosphate, phosphite ester, acid phosphite, alkyl hydrogen phosphite, phosphate ester amine salt, phosphite amine salt, etc.
- Phosphorus compounds chlorinated oils and fats, chlorinated paraffins, chlorinated fatty acid esters, chlorinated fatty acid esters and other chlorinated compounds, alkyl or alkenyl maleic acid esters, alkyl or alkenyl succinic acid ester compounds, alkyl or alkenyl maleic acids And organic acid compounds such as alkyl or alkenyl succinic acid, and organic metal compounds such as naphthenate.
- solid lubricant examples include polyimide, PTFE, graphite, metal oxide, boron nitride, melamine cyanurate (MCA), and molybdenum disulfide.
- MCA melamine cyanurate
- the various additives as described above may be blended alone or in combination, and the lubricating oil additive of the present invention does not inhibit these effects.
- FIG. 1 is a schematic view showing a wind power generator in which the grease composition of the present invention is used.
- a wind turbine generator 1 is connected to a wing 5, a main shaft 4 to which the wing 5 is fixed, a generator 31 driven by the rotation of the main shaft 4, and the main shaft 4.
- a nacelle 3 for housing the main bearing 33 and the yaw bearing 32 and a tower 2 for supporting the nacelle 3 are provided.
- a pitch bearing 41 is connected to the wing shaft 51. For example, by rotating the wing shaft 51, it is possible to make the wing 5 easier to receive or not receive wind, so that the rotation of the main shaft 4 becomes constant. Thereby, stable electric power can be obtained from the generator 31.
- the grease composition of the present invention is preferably used for the main bearing 33 and the pitch bearing 41.
- wear of the roller, cage, bearing race, and the like due to heavy loads caused by the heavy wings 5 and the main shaft 4, or fretting of the bearing race due to fluctuations and swings of rotation, etc.
- bearing wear and fretting wear can be prevented by using the grease of the present invention.
- the wind turbine generator 1 is less effective when the output is smaller than 300 kW because the load is small.
- the wind power generator 1 is preferably a medium or large size having an output of 300 kW or more, more preferably 700 kW or more.
- the main bearing 33 and the pitch bearing 41 may be connected to a pump for supplying grease via a pipe (not shown). The grease can be easily supplied to the main bearing 33 and the pitch bearing 41 by operating the pump. For this reason, work at a high place becomes unnecessary, and workability is improved.
- the grease composition of the present invention includes various gears, various bearings (ball bearings, roller bearings, slide bearings, pin-bushes, etc.), paper machine rollers, steel equipment bearings, construction machine slewing bearings, It can be used for geared motors, automobile wheel bearings, generator bearings, motor bearings, ball screws and the like.
- it is a device that performs rolling motion, such as a rolling bearing, a ball screw, a linear guide, etc., and may be used for high load applications.
- it can be used for an electric cylinder, an electric linear actuator, a jack, a linear actuator, and the like.
- a component in Table 1 is the poly alpha olefin manufactured using the metallocene catalyst.
- M-PAO-400 and M-PAO-1200 used in this example were manufactured by the following method.
- M-PAO-400 A stainless steel reactor with an internal volume of 107 liters was thoroughly dried, and after nitrogen substitution, 16.6 liters of 1-octene, 23.4 liters of 1-dodecene, and then 20 mmol of triisobutylaluminum were added, and the temperature was raised to 105 ° C. did.
- the contents were withdrawn 20 liters into two 100 L stainless steel containers, 20 liters of toluene and 20 liters of a 1% by weight NaOH aqueous solution were added to each container, and stirred for 1 hour. After allowing to stand for 1 hour, the aqueous phase was extracted, 20 liters of pure water was newly added, stirred for 1 hour, and then allowed to stand for 1 hour to extract the aqueous phase. This operation was repeated twice. The organic layer was filtered through a 2 micrometer filter, then transferred to a stainless steel reactor with an internal volume of 107 liters, and light, such as toluene, raw materials, methanol, etc. at 140 ° C.
- M-PAO-1200 Except for the polymerization temperature of 90 ° C., in the same manner as in the production of M-PAO-400, after obtaining 24.2 kg of a colorless and transparent viscous liquid from which light components were removed, components having 20 or less carbon atoms were completely removed. 4.7 kg of a colorless and transparent viscous liquid was removed, and 3.0 kg of hydride (M-PAO-1200) was obtained.
- Examples 1 to 5 and Comparative Example 1 (1) PAO-30 [or M-PAO-30, M-PAO-45], 12-hydroxystearic acid, azelaic acid and an antirust agent in the amounts shown in Table 1 were stirred in a reaction kettle. Heated to ° C. (2) Lithium hydroxide (monohydrate) was dissolved in 5 times the amount (mass ratio) of water. This aqueous solution was added to the solution of (1) and mixed by heating. After the temperature of the mixture reached 195 ° C., it was held for 5 minutes. (3) Next, the remaining base oil (M-PAO-1200 or M-PAO-400, or olefin oligomer) was added, and then cooled to 80 ° C. at 50 ° C./hour. Antioxidant and extreme pressure agent were added and mixed. (4) Further, after naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Examples 1 to 5 and Comparative Example 1.
- Comparative Examples 2-4 (1) A part of the base oil shown in Table 2 (50% by mass with respect to the finished grease amount) and the amounts of 12-hydroxystearic acid, azelaic acid and rust inhibitor shown in Table 2 in the reaction kettle. And heated to 95 ° C. with stirring. (2) Lithium hydroxide (monohydrate) was dissolved in 5 times the amount (mass ratio) of water. This aqueous solution was added to the solution of (1) and mixed by heating. After the temperature of the mixture reached 195 ° C., it was held for 5 minutes. (3) Next, after the remaining base oil was added, it was cooled to 80 ° C. at 50 ° C./hour, and the amounts of antioxidant and extreme pressure agent shown in Table 1 were added and mixed. (4) Further, after naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Comparative Examples 2 to 4.
- Example 6 and Comparative Example 5 (1) 1 mol of diphenylmethane-4,4′-diisocyanate (MDI) was heated and dissolved to 2/3 mass of the total amount of the base oil to obtain raw material 1. (2) Further, 2 mol of cyclohexylamine was stirred and dissolved in the remaining base oil to obtain raw material 2. (3) Next, the raw material 2 was gradually added while vigorously stirring the raw material 1 at 50 to 60 ° C. in a grease reaction kettle. The mixture was heated while stirring, and held for 1 hour after the temperature of the grease composition reached 165 ° C. (4) Thereafter, the mixture was cooled to 80 ° C. at 50 ° C./hour, and the amounts of antioxidant and extreme pressure agent shown in Table 1 were added and mixed.
- MDI diphenylmethane-4,4′-diisocyanate
- Example 6 After naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Example 6 and Comparative Example 5. The following properties of the grease compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated. The results are shown in Table 2.
- the thickener blending amount was defined as the amount of carboxylic acid (12-hydroxystearic acid + azelenic acid).
- Low temperature torque test Measured by the method defined in JIS K 2220.18. The temperature was ⁇ 40 ° C.
- High-load bearing wear test Measured by the method specified in DIN51819-2. (Test conditions DIN51819-2-C-75 / 50-120, load 50KN, temperature 120 ° C, rotation speed 75rpm) Test the weight of the bearing ring (inner ring + outer ring), rolling elements (total of 16 rollers), and cage Measured before and after, the respective weight loss per bearing was determined as 50% probability of wear as defined in DIN 51819-2.11.
- the grease composition of the present invention includes various gears, various bearings (ball bearings, roller bearings, sliding bearings, pin-bushings, etc.), paper machine rollers, steel equipment bearings, construction machine slewing bearings, geared motors, automobile wheel bearings, although it can be used for a generator bearing, a motor bearing, a ball screw, etc., it can be suitably used especially as a grease composition used for a main bearing and a pitch bearing incorporated in a wind power generator.
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Abstract
Description
そこで、耐フレッチング性の向上を目的として、100℃における動粘度が200~2500mm2/sであるエステル系合成油を基油としたグリース組成物が提案されている(特許文献1参照)。
さらに、大きな荷重に対して、耐久性を向上させるために、グリース組成物用として高粘度基油を使用し、必要に応じ極圧剤を配合したグリース組成物も開示されている(非特許文献1,2参照)。
また、風力発電装置に使用されるグリース組成物としては、基油と増ちょう剤とオレオイルザルコシンとを含んだ組成物(特許文献2参照)や、40℃における動粘度が70~250mm2/sである基油と増ちょう剤とカルボン酸系防錆添加剤とを含有する組成物が提案されている(特許文献3参照)。 For example, a grease composition is used for lubrication of a bearing that receives a large load, such as a main bearing that receives a main shaft and a pitch bearing that receives a blade shaft incorporated in a wind power generator. Such main bearings and pitch bearings are constantly subject to fluctuations and minute fluctuations due to changes in wind speed and minute control of the blades, and are in an environment where fretting wear is likely to occur. Replacing a bearing in the event of a failure requires great effort and cost, and therefore a lubricant that has excellent fretting resistance and is unlikely to cause damage to the bearing over a long period of time is required.
Therefore, for the purpose of improving the fretting resistance, a grease composition based on an ester synthetic oil having a kinematic viscosity at 100 ° C. of 200 to 2500 mm 2 / s has been proposed (see Patent Document 1).
Furthermore, a grease composition is disclosed that uses a high-viscosity base oil for a grease composition and, if necessary, contains an extreme pressure agent to improve durability against a large load (non-patent document). 1 and 2).
In addition, examples of the grease composition used in the wind power generator include a composition containing a base oil, a thickener, and oleoyl sarcosine (see Patent Document 2), and a kinematic viscosity at 40 ° C. of 70 to 250 mm 2. A composition containing a base oil that is / s, a thickener, and a carboxylic acid-based anticorrosive additive has been proposed (see Patent Document 3).
また、本発明の課題は、揺動方向への微小振動に伴うフレッチング摩耗に加え、スラスト方向の荷重変動に伴うフレッチング摩耗を抑制しうるグリース組成物を提供することにある。
さらに、本発明の課題は、低温特性に優れるグリース組成物を提供することにある。 An object of the present invention is to provide a grease composition capable of simultaneously suppressing bearing wear and fretting wear under a high load and extending the life of the bearing.
Another object of the present invention is to provide a grease composition that can suppress fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swinging direction.
Furthermore, the subject of this invention is providing the grease composition which is excellent in a low-temperature characteristic.
(1)基油及び増ちょう剤を含むグリース組成物であって、前記基油が、40℃における動粘度が300mm2/s以上の、メタロセン触媒を用いて製造されたポリ-α-オレフィン(A成分)を含有するグリース組成物、
(2)前記A成分の40℃における動粘度が600mm2/s以上である、前記(1)記載のグリース組成物、
(3)前記A成分を、組成物全量基準で20質量%以上含有する、前記(1)または(2)に記載のグリース組成物、
(4)前記基油の40℃における動粘度が150~2000mm2/sであって、混和ちょう度が220~385である、前記(1)~(3)のいずれかに記載のグリース組成物、
(5)前記基油が、40℃における動粘度が70mm2/s以下であるB成分を、組成物全量基準で10~70質量%含有する、前記(1)~(4)のいずれかに記載のグリース組成物、 The present invention
(1) A grease composition containing a base oil and a thickening agent, wherein the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a poly-α-olefin ( A grease composition containing component A),
(2) The grease composition according to (1), wherein the kinematic viscosity of the component A at 40 ° C. is 600 mm 2 / s or more,
(3) The grease composition according to (1) or (2), wherein the component A is contained in an amount of 20% by mass or more based on the total amount of the composition,
(4) The grease composition according to any one of (1) to (3) above, wherein the base oil has a kinematic viscosity at 40 ° C. of 150 to 2000 mm 2 / s and a penetration of 220 to 385. ,
(5) In any one of (1) to (4), the base oil contains 10 to 70% by mass of a B component having a kinematic viscosity at 40 ° C. of 70 mm 2 / s or less based on the total amount of the composition. The grease composition as described,
(7)前記増ちょう剤が石けん系増ちょう剤である、前記(1)~(6)のいずれかに記載のグリース組成物、
(8)前記増ちょう剤が、前記B成分中にてカルボン酸とアルカリとの反応を行うことにより製造された、前記(1)~(7)のいずれかに記載のグリース組成物、
(9)硫黄を含む極圧添加剤が組成物全量基準で0.01~10質量%配合されている、前記(1)~(8)のいずれかに記載のグリース組成物、及び
(10)風力発電装置に使用されるグリース組成物であって、該風力発電装置の羽が連結された主軸に連接されたメインベアリング、及び、前記羽に組み込まれた羽軸に連接されたピッチベアリングのうち少なくとも一方に使用される、前記(1)~(9)のいずれかに記載のグリース組成物、
に関する。 (6) The grease composition according to any one of (1) to (5), wherein the thickener is contained in an amount of 17% by mass or less based on the total amount of the composition,
(7) The grease composition according to any one of (1) to (6), wherein the thickener is a soap-based thickener,
(8) The grease composition according to any one of (1) to (7), wherein the thickener is produced by reacting a carboxylic acid and an alkali in the component B.
(9) The grease composition according to any one of (1) to (8), wherein the extreme pressure additive containing sulfur is blended in an amount of 0.01 to 10% by mass based on the total amount of the composition, and (10) A grease composition used for a wind power generator, comprising: a main bearing connected to a main shaft to which a wing of the wind power generator is connected; and a pitch bearing connected to a wing shaft incorporated in the wing. The grease composition according to any one of (1) to (9), which is used for at least one of the above,
About.
また、本発明によれば、揺動方向への微小振動に伴うフレッチング摩耗に加え、スラスト方向の荷重変動に伴うフレッチング摩耗を抑制しうるグリース組成物を提供することができ、さらに、低温トルクが小さく、低温特性に優れるグリース組成物を提供することができる。 According to the grease composition of the present invention, bearing wear and fretting wear under a high load can be simultaneously suppressed, and the life of the bearing can be extended.
Further, according to the present invention, it is possible to provide a grease composition capable of suppressing fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swinging direction. A grease composition that is small and excellent in low-temperature characteristics can be provided.
[A成分]
本発明のグリース組成物は、基油及び増ちょう剤を含み、基油は、40℃における動粘度が300mm2/s以上の、メタロセン触媒を用いて製造されたポリ-α-オレフィン(A成分)を含有する。
本発明において、メタロセン触媒を用いて製造されたポリ-α-オレフィンとしては、軸受摩耗及びフレッチング摩耗を同時に抑制し、軸受の長寿命化を図ること、特に揺動方向への微小振動に伴うフレッチング摩耗に加え、スラスト方向の荷重変動に伴うフレッチング摩耗を抑制しうる観点から、40℃における動粘度が300mm2/s以上のものが用いられる。 Hereinafter, the present invention will be described more specifically.
[Component A]
The grease composition of the present invention comprises a base oil and a thickener, and the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a poly-α-olefin (component A). ).
In the present invention, the poly-α-olefin produced using a metallocene catalyst can suppress bearing wear and fretting wear at the same time, thereby prolonging the life of the bearing, particularly fretting caused by minute vibration in the swinging direction. In addition to wear, those having a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more are used from the viewpoint of suppressing fretting wear associated with load fluctuations in the thrust direction.
(RC5H4)2MX2 (I)
で表されるメタロセン化合物が好ましい。一般式(I)中、Rは水素原子または炭素数1~10の炭化水素基を表し、Mは周期律表第4族の遷移金属元素を表し、Xは共有結合性、又はイオン結合性の配位子を表す。 Examples of the metallocene catalyst for obtaining the component A include a catalyst containing a combination of a metallocene compound and a promoter. As the metallocene compound, a compound represented by the general formula (I)
(RC 5 H 4 ) 2 MX 2 (I)
The metallocene compound represented by these is preferable. In general formula (I), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a transition metal element of Group 4 of the periodic table, and X represents a covalent bond or an ionic bond. Represents a ligand.
メチルアルミノキサンの製造法としては、メチルアルミニウムと水などの縮合剤とを接触させる方法が挙げられるが、その手段については特に制限はなく、公知の方法に準じて行えばよい。 The chain | strand-shaped or cyclic | annular methylaluminoxane represented by these is mentioned. In the general formulas (II) and (III), p represents the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.
Examples of the method for producing methylaluminoxane include a method in which methylaluminum and a condensing agent such as water are brought into contact with each other, but the means is not particularly limited and may be carried out according to a known method.
なお、前記メソ対称型の化合物とは、2つの架橋基が(1,1’)(2,2’)の結合様式で、2つのEを架橋する遷移金属化合物のことをいう。 The compound represented by the formula (IV) is a mesosymmetric compound, and in the formula (IV), M represents a metal element belonging to Groups 3 to 10 of the periodic table. X represents a σ-binding ligand, and when there are a plurality of X, a plurality of X may be the same or different, Y represents a Lewis base, and when there are a plurality of Y, a plurality of Y are the same or different It may be. A represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, — SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - and -AlR 1 - shows a bridging group selected from 2 in the formula (IV) Two A's may be the same or different. R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. E is a group represented by the following formulas (V) and (VI), and two Es in the formula (IV) are the same.
The mesosymmetric compound refers to a transition metal compound in which two bridging groups bridge two Es in a bonding mode of (1,1 ′) (2,2 ′).
(〔L1-R4〕k+)a(〔Z〕-)b・・・(VIII)
(〔L2〕k+)a(〔Z〕-)b・・・(IX) As the component (b-1) of the component (b), any compound can be used as long as it can react with the metallocene compound of the component (a) to form an ionic complex. Those represented by the following general formulas (VIII) and (IX) can be preferably used.
([L 1 −R 4 ] k + ) a ([Z] − ) b (VIII)
([L 2 ] k + ) a ([Z] − ) b (IX)
(b-1)は一種用いてもよく、又二種以上を組み合わせて用いてもよい。 Specific examples of such an ionic compound that reacts with the metallocene compound (a) to form an ionic complex, ie, (b-1) component compound, include tetrakis (pentafluorophenylboric acid) N, N -Dimethylanilinium, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (Tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methyl tetraphenylborate Pyridinium, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) boric acid Triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) benzyl borate (tri-n-butyl) ammonium, tetrakis (pentafluorophenyl) ) Methyldiphenylammonium borate, tetrakis (pentafluorophenyl) triphenyl (methyl) ammonium borate Um, tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) dimethylanilinium borate, tetrakis (pentafluorophenyl) trimethylanilinium borate, tetrakis (pentafluorophenyl) methylpyridinium borate, tetrakis (pentafluorophenyl) ) Benzylpyridinium borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyltetrakis (pentafluorophenyl) benzyl borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), Tetrakis (pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate Dimethylanilinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1'-dimethyl) Ferrocenium), tetrakis (pentafluorophenyl) decamethyl ferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) ) Sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, hexafluoro Examples thereof include silver phosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.
(B-1) may be used alone or in combination of two or more.
例えば、(1)有機アルミニウム化合物を有機溶剤に溶解しておき、これを水と接触させる方法、(2)重合時に当初有機アルミニウム化合物を加えておき、後に水を添加する方法、(3)金属塩などに含有されている結晶水、無機物や有機物への吸着水を有機アルミニウム化合物と反応させる方法、(4)テトラアルキルジアルミノキサンにトリアルキルアルミニウムを反応させ、更に水を反応させる方法などがある。尚、アルミノキサンとしては、トルエン不溶性のものであってもよい。これらのアルミノキサンは一種用いてもよく、二種以上を組み合わせて用いてもよい。 Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There are a method for reacting water adsorbed on salts and the like, water adsorbed on inorganic substances and organic substances with organoaluminum compounds, and (4) a method for reacting tetraalkyldialuminoxane with trialkylaluminum and further reacting with water. . The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.
(R20)vAlQ3-v ・・・(XII)
(式中、R20は炭素数1~10のアルキル基、Qは水素原子、炭素数1~20のアルコキシ基,炭素数6~20のアリール基又はハロゲン原子を示し、vは1~3の整数である。)で示される化合物が用いられる。 The catalyst in the present invention may contain the components (a) and (b) as main components, and (a) component, (b) component and (c) organoaluminum compound. May be contained as a main component. Here, as the organoaluminum compound of component (c), the general formula (XII)
(R 20 ) v AlQ 3-v (XII)
(Wherein R 20 represents an alkyl group having 1 to 10 carbon atoms, Q represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms) Which is an integer).
このため、本発明のグリース組成物は、粘度指数が高くなることで、従来のポリα-オレフィンを使用するグリース組成物とは異なり、低温粘度特性が向上するとともに、粘度指数向上剤への依存度が下がる。この結果、本発明のグリース組成物は、揺動方向への微小振動に伴うフレッチング摩耗に加え、スラスト方向の荷重変動に伴うフレッチング摩耗をも抑制しうる。 Thus, component A is different from conventional poly α-olefins in terms of molecular structure and high homogeneity, and exhibits high oxidation stability and high viscosity index, and is excellent as a lubricating base oil. . The viscosity index of the component A is preferably from 150 to 350, more preferably from 165 to 300, from the viewpoint of increasing fluidity at low temperatures.
For this reason, the grease composition of the present invention has a high viscosity index, which, unlike conventional grease compositions using poly α-olefins, improves low-temperature viscosity characteristics and depends on a viscosity index improver. The degree goes down. As a result, the grease composition of the present invention can also suppress fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swing direction.
本発明のグリース組成物には、上記A成分とともに、フレッチング摩耗や圧送性を改善する観点から、40℃における動粘度が70mm2/s以下であるB成分を含有することが好ましい。上記観点から、B成分の40℃における動粘度は、好ましくは10~50mm2/sであり、より好ましくは20~45mm2/s、さらに好ましくは20~40mm2/sである。B成分の100℃における動粘度は13mm2/s以下であることが好ましく、より好ましくは3~9mm2/sである。また、B成分の粘度指数は、低温での流動性を高める観点から、70~250であることが好ましく、120~200であることがより好ましい。 [B component]
From the viewpoint of improving fretting wear and pumpability, the grease composition of the present invention preferably contains a B component having a kinematic viscosity at 40 ° C. of 70 mm 2 / s or less from the viewpoint of improving fretting wear and pumpability. From the above viewpoint, the kinematic viscosity at 40 ° C. of the component B is preferably 10 to 50 mm 2 / s, more preferably 20 to 45 mm 2 / s, and still more preferably 20 to 40 mm 2 / s. The kinematic viscosity at 100 ° C. of the component B is preferably 13 mm 2 / s or less, more preferably 3 to 9 mm 2 / s. Further, the viscosity index of the component B is preferably from 70 to 250, more preferably from 120 to 200, from the viewpoint of improving fluidity at low temperatures.
基油は、上記A成分及び好ましくはB成分に、さらに必要に応じ、他の合成油や鉱油を含んでいてもよい。 [Base oil]
The base oil may further contain other synthetic oil or mineral oil, if necessary, in the A component and preferably the B component.
上記の合成油は、それぞれ単独で使用してもよく、混合物として使用してもよい。 Examples of other synthetic oils include, as aromatic oils, alkylbenzenes such as monoalkylbenzene and dialkylbenzene, and alkylnaphthalenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene. Examples of ester oils include dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, ditridecyl glutarate, and methyl acetyl cinnolate, or trioctyl trimellitate, Aromatic ester oils such as tridecyl trimellitate and tetraoctyl pyromellitate, and further trimethylolpropane caprylate, trimethylolpropane verargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol verargonate, etc. Polyol ester oils, and complex ester oils that are oligoesters of polyhydric alcohols and mixed fatty acids of dibasic acids and monobasic acids are also exemplified. Examples of ether oils include polyglycols such as polyethylene glycol, polypropylene glycol, polyethylene glycol monoether, and polypropylene glycol monoether, or monoalkyl triphenyl ether, alkyl diphenyl ether, dialkyl diphenyl ether, pentaphenyl ether, tetraphenyl ether, monoalkyl tetra Examples thereof include phenyl ether oils such as phenyl ether and dialkyl tetraphenyl ether, olefinic oligomers such as normal paraffin, isoparaffin, polybutene, polyisobutylene, 1-decene oligomer, and 1-decene and ethylene co-oligomer.
The above synthetic oils may be used alone or as a mixture.
本発明のグリース組成物は増ちょう剤を含有するが、増ちょう剤としては、有機系及び無機系の何れの増ちょう剤も使用でき、耐摩耗性の観点から、石けん系増ちょう剤が好ましい。具体的には、好ましくは、Li石けん、Liコンプレックス石けん、Ca石けん、Caスルホネートコンプレックス石けん,Caコンプレックス石けんのいずれかであり、より好ましくは、石けんを構成する脂肪酸に12-ヒドロキシステアリン酸塩を含むものである。中でも、石けんは、Liを含むことが好ましく、更に好ましくは、Liコンプレックス石けんである。Liコンプレックス石けんは低温から高温までの性能バランスに優れる。
また、増ちょう剤としては、ウレア化合物、ベントナイト、シリカ、カーボンブラック、PTFE等を使用してもよい。また、これらは単独でも、混合して使用してもよい。 [Thickener]
The grease composition of the present invention contains a thickener. As the thickener, both organic and inorganic thickeners can be used, and a soap-based thickener is preferable from the viewpoint of wear resistance. . Specifically, Li soap, Li complex soap, Ca soap, Ca sulfonate complex soap, or Ca complex soap is more preferable. More preferably, the fatty acid constituting the soap contains 12-hydroxystearate. It is a waste. Especially, it is preferable that soap contains Li, More preferably, it is Li complex soap. Li complex soap is excellent in performance balance from low temperature to high temperature.
As the thickener, urea compounds, bentonite, silica, carbon black, PTFE, etc. may be used. These may be used alone or in combination.
ここで、増ちょう剤の含有量とは、石けん系増ちょう剤については、増ちょう剤を構成するカルボン酸の量として表す。ウレア系増ちょう剤は、イソシアネートとアミンの反応物量として表す。 The content of the thickener is not limited as long as grease can be formed and maintained with the above base oil, but in addition to fretting wear due to minute vibrations in the swing direction, fretting wear due to load fluctuations in the thrust direction. From the viewpoint of suppressing the amount and the excellent pumpability, it is preferably 17% by mass or less based on the total amount of the composition of the present invention. From the above viewpoint, the blending amount of the thickener is more preferably 14% by mass or less, and particularly preferably 12% by mass or less, based on the total amount of the composition.
Here, the content of the thickener is expressed as the amount of carboxylic acid constituting the thickener for the soap-type thickener. The urea-based thickener is expressed as a reaction amount of isocyanate and amine.
カルボン酸としては、油脂を加水分解してグリセリンを除いた粗製脂肪酸、ステアリン酸等のモノカルボン酸や、12-ヒドロキシステアリン酸等のモノヒドロキシカルボン酸、アゼライン酸等の二塩基酸、テレフタル酸、サルチル酸、安息香酸等の芳香族カルボン酸などが挙げられる。なお、カルボン酸のエステルを使用してもよい。これらは、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
上記アルカリとしては、アルカリ金属あるいはアルカリ土類金属等の金属水酸化物が挙げられる。金属としては、ナトリウム、カルシウム、リチウム、アルミニウム等が挙げられる。 Moreover, as a manufacturing method of a thickener, it is preferable to obtain a thickener by mixing carboxylic acid and an alkali in B component of base oil, and performing a saponification reaction.
Carboxylic acids include crude fatty acids obtained by hydrolyzing fats and oils to remove glycerol, monocarboxylic acids such as stearic acid, monohydroxycarboxylic acids such as 12-hydroxystearic acid, dibasic acids such as azelaic acid, terephthalic acid, Examples include aromatic carboxylic acids such as salicylic acid and benzoic acid. In addition, you may use ester of carboxylic acid. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the alkali include metal hydroxides such as alkali metals or alkaline earth metals. Examples of the metal include sodium, calcium, lithium, and aluminum.
本発明のグリース組成物には、硫黄を含む極圧剤を、焼付きの防止などの配合効果を得る観点から組成物全量基準で0.01~10質量%配合することが好ましい。
このような極圧剤としては、ジアルキルジチオリン酸亜鉛(ZnDTP)、ジアルキルジチオリン酸モリブデン(MoDTP)、ジチオカルバミン酸亜鉛(ZnDTC)、ジチオカルバミン酸モリブデン(MoDTC)、ジチオカルバミン(DTC)、チオフォスフェート、硫化油脂、二硫化ジベンジル、チアジアゾールなどが挙げられる。これらの化合物は、1種単独で用いても良いし、2種以上を混合して用いても良い。 [Other ingredients]
In the grease composition of the present invention, an extreme pressure agent containing sulfur is preferably blended in an amount of 0.01 to 10% by mass based on the total amount of the composition from the viewpoint of obtaining blending effects such as prevention of seizure.
Examples of such extreme pressure agents include zinc dialkyldithiophosphate (ZnDTP), molybdenum dialkyldithiophosphate (MoDTP), zinc dithiocarbamate (ZnDTC), molybdenum dithiocarbamate (MoDTC), dithiocarbamine (DTC), thiophosphate, sulfurized oil, Examples include dibenzyl disulfide and thiadiazole. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
上記のシクロペンタジエン類としては、シクロペンタジエン、その多量体、それらのアルキル置換体、あるいはそれらの混合物を用いることができ、工業的にはナフサ等のスチームクラッキングにより得られるシクロペンタジエン類を約30質量%以上、好ましくは約50質量%以上含むシクロペンタジエン系留分(CPD留分)を用いることが有利である。このCPD留分は、これら脂環式ジエンと共重合可能なオレフィン性単量体を含んでいてもよい。このオレフィン性単量体としては、イソプレン、ピペリレンあるいはブタジエン等の脂肪族ジオレフィン、シクロペンテン等の脂環式オレフィンなどが挙げられる。これらオレフィン類の濃度は、低い方が好ましいが、シクロペンタジエン類当たり約10質量%以下であれば許容される。 As the petroleum resin, for example, a cyclopentadiene type is preferable, a product obtained by thermal copolymerization of a cyclopentadiene and an α-olefin or a monovinyl aromatic hydrocarbon, and a product obtained by hydrogenating these by a usual method as necessary. Or a mixture thereof.
As the cyclopentadiene, cyclopentadiene, a multimer thereof, an alkyl-substituted product thereof, or a mixture thereof can be used. Industrially, about 30 mass of cyclopentadiene obtained by steam cracking such as naphtha is used. It is advantageous to use a cyclopentadiene fraction (CPD fraction) containing at least%, preferably at least about 50% by weight. This CPD fraction may contain an olefin monomer copolymerizable with these alicyclic dienes. Examples of the olefinic monomer include aliphatic diolefins such as isoprene, piperylene and butadiene, and alicyclic olefins such as cyclopentene. The concentration of these olefins is preferably low, but is acceptable if it is about 10% by mass or less per cyclopentadiene.
本発明のグリース組成物は、グリースの硬さを調整し良好な低温トルク特性を維持し、軸受摩耗、フレッチング摩耗を防止する観点から、混和ちょう度が220~350であることが好ましい。上記観点から、混和ちょう度は好ましくは250~340であり、さらに好ましくは265~320である。 [Grease composition]
The grease composition of the present invention preferably has a blending degree of 220 to 350 from the viewpoint of adjusting the hardness of the grease to maintain good low temperature torque characteristics and preventing bearing wear and fretting wear. From the above viewpoint, the penetration is preferably 250 to 340, more preferably 265 to 320.
酸化防止剤としては、例えばアルキル化ジフェニルアミン、フェニル-α-ナフチルアミン、アルキル化-α-ナフチルアミン等のアミン系酸化防止剤、2,6-ジ-t-ブチル-4-メチルフェノール、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)等のフェノール系酸化防止剤、硫黄系・ZnDTPなどの過酸化物分解剤等が挙げられ、これらは、通常0.05~10質量%の割合で使用される。 In the grease composition of the present invention, an antioxidant, a rust preventive agent, a solid lubricant, a filler, an oily agent, a metal deactivator, if necessary, within the range where the object of the present invention is achieved. You may mix | blend additives, such as a water-resistant agent, another extreme pressure agent, an antiwear agent, a viscosity index improver, and a coloring agent.
Examples of the antioxidant include amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated-α-naphthylamine, 2,6-di-t-butyl-4-methylphenol, 4,4 ′ -Phenolic antioxidants such as methylene bis (2,6-di-t-butylphenol), peroxide decomposition agents such as sulfur and ZnDTP, etc., and these are usually in the proportion of 0.05 to 10% by mass Used in.
他の極圧剤、耐摩耗剤としては、例えば、リン酸エステル、アシッドフォスフェート、亜リン酸エステル、アシッドフォスファイト、アルキルハイドロゲンホスファイト、リン酸エステルアミン塩、亜リン酸エステルアミン塩などのリン系化合物、塩素化油脂、塩素化パラフィン、塩素化脂肪酸エステル、塩素化脂肪酸などの塩素系化合物、アルキル若しくはアルケニルマレイン酸エステル、アルキル若しくはアルケニルコハク酸エステルなどのエステル系化合物、アルキル若しくはアルケニルマレイン酸、アルキル若しくはアルケニルコハク酸などの有機酸系化合物、ナフテン酸塩などの有機金属系化合物などが挙げられる。 Examples of the rust inhibitor include sodium nitrite, sulfonate, sorbitan monooleate, fatty acid soap, amine compound, succinic acid derivative, thiadiazole, benzotriazole, and benzotriazole derivative.
Other extreme pressure agents and antiwear agents include, for example, phosphate ester, acid phosphate, phosphite ester, acid phosphite, alkyl hydrogen phosphite, phosphate ester amine salt, phosphite amine salt, etc. Phosphorus compounds, chlorinated oils and fats, chlorinated paraffins, chlorinated fatty acid esters, chlorinated fatty acid esters and other chlorinated compounds, alkyl or alkenyl maleic acid esters, alkyl or alkenyl succinic acid ester compounds, alkyl or alkenyl maleic acids And organic acid compounds such as alkyl or alkenyl succinic acid, and organic metal compounds such as naphthenate.
本発明のグリース組成物は、風力発電装置に好適に使用される。図1は、本発明のグリース組成物が使用される風力発電装置を示す概略図である。図1に示すように、このような風力発電装置1は、羽5と、この羽5を固定した主軸4と、この主軸4の回転によって駆動される発電機31と、主軸4に連接されたメインベアリング33及びヨーベアリング32を収納するナセル3と、ナセル3を支持するタワー2とを備えている。また、羽軸51には、ピッチベアリング41が連接される。例えば、羽軸51を回転させることにより、羽5に風を受けやすくさせたり、受けにくくさせることができるため、主軸4の回転が一定となる。これにより、発電機31から安定した電力を得ることができる。 [Grease composition for wind power generation]
The grease composition of the present invention is suitably used for a wind power generator. FIG. 1 is a schematic view showing a wind power generator in which the grease composition of the present invention is used. As shown in FIG. 1, such a wind turbine generator 1 is connected to a
また、メインベアリング33及びピッチベアリング41には、図示しないパイプを介してグリースを供給するためのポンプが接続されていてもよい。ポンプを作動させることにより、簡単にメインベアリング33及びピッチベアリング41にグリースを供給することができる。そのため、高所での作業が不要になり、作業性が向上する。 The grease composition of the present invention is preferably used for the
The
特に、ころがり軸受、ボールネジ、リニアガイド等、転がり運動を行う装置であって、高荷重用途に使用されても良い。例えば、電動シリンダ、電動式リニアアクチュエータ、ジャッキ、直線作動機などに用いることができる。 In addition to wind power generators, the grease composition of the present invention includes various gears, various bearings (ball bearings, roller bearings, slide bearings, pin-bushes, etc.), paper machine rollers, steel equipment bearings, construction machine slewing bearings, It can be used for geared motors, automobile wheel bearings, generator bearings, motor bearings, ball screws and the like.
In particular, it is a device that performs rolling motion, such as a rolling bearing, a ball screw, a linear guide, etc., and may be used for high load applications. For example, it can be used for an electric cylinder, an electric linear actuator, a jack, a linear actuator, and the like.
内容積107リットルのステンレス製反応器を十分乾燥し、窒素置換の後に、1-オクテン16.6リットルと1-ドデセン23.4リットル、次にトリイソブチルアルミニウム20ミリモルをいれ、105℃に昇温した。別途準備した触媒混合液(容積2リットルのガラス製シュレンク瓶に窒素雰囲気下で脱水トルエン700ミリリットル、トリイソブチルアルミニウム40ミリモル、(1,1’-ジメチルシリレン)(2,2’-ジメチルシリレン)-ビス(シクロペンタジエニル)ジルコニウムジクロリド0.8ミリモル及び粉末状のN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート1.6ミリモルを入れ室温で1分ほど攪拌した後、1-デセン100ミリリットルを加えて更に室温で1時間攪拌したもの)を80ミリリットル投入後、水素0.02MPaGを導入し、温度を107℃に上げて重合を開始した。以降60分毎に触媒混合液80ミリリットルを添加し、107℃で300分反応させた後、メタノール100ミリリットルを投入し重合を停止させた。 M-PAO-400
A stainless steel reactor with an internal volume of 107 liters was thoroughly dried, and after nitrogen substitution, 16.6 liters of 1-octene, 23.4 liters of 1-dodecene, and then 20 mmol of triisobutylaluminum were added, and the temperature was raised to 105 ° C. did. Separately prepared catalyst mixture (700 ml of dehydrated toluene, 40 mmol of triisobutylaluminum, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) in a 2 liter glass Schlenk bottle under nitrogen atmosphere) After adding 0.8 mmol of bis (cyclopentadienyl) zirconium dichloride and 1.6 mmol of powdered N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and stirring for about 1 minute at room temperature, 1-decene 100 After adding 80 milliliters, the mixture was stirred at room temperature for 1 hour, 0.02 MPaG of hydrogen was introduced, and the temperature was raised to 107 ° C. to initiate polymerization. Thereafter, 80 ml of the catalyst mixture was added every 60 minutes and reacted at 107 ° C. for 300 minutes, and then 100 ml of methanol was added to stop the polymerization.
得られた粘性液体3.0キログラムを内容積5リットルのステンレス製オートクレーブに入れ、安定化ニッケル触媒(堺化学工業株式会社製 SN750)を重量比で1質量%添加後、2MPaの水素のもと130℃で6時間反応させた。反応終了後、温度を80℃付近まで冷却した後、内容物を取り出し、1μmのフルターを用いて70℃で触媒成分を濾過分離し、水素化物(M-PAO―400)3.0キログラムを得た。 The contents were withdrawn 20 liters into two 100 L stainless steel containers, 20 liters of toluene and 20 liters of a 1% by weight NaOH aqueous solution were added to each container, and stirred for 1 hour. After allowing to stand for 1 hour, the aqueous phase was extracted, 20 liters of pure water was newly added, stirred for 1 hour, and then allowed to stand for 1 hour to extract the aqueous phase. This operation was repeated twice. The organic layer was filtered through a 2 micrometer filter, then transferred to a stainless steel reactor with an internal volume of 107 liters, and light, such as toluene, raw materials, methanol, etc. at 140 ° C. under a reduced pressure of about 3.0 × 10 −1 MPa. The components were distilled off to obtain 23.1 kg of a colorless and transparent viscous liquid. Using 5 kg of the obtained viscous liquid, distillation was performed at 180 ° C. under a reduced pressure of 5 × 10 −6 MPa using a thin film distillation apparatus (short-path distillation apparatus KDL-5 manufactured by UIC), and a component having 20 or less carbon atoms was obtained. 4.5 kg of a colorless and transparent viscous liquid which was completely removed was obtained.
3.0 kg of the obtained viscous liquid was put into a stainless steel autoclave having an internal volume of 5 liters, and 1 wt% of a stabilized nickel catalyst (SN750, manufactured by Sakai Chemical Industry Co., Ltd.) was added at a weight ratio of 2 MPa under hydrogen. The reaction was carried out at 130 ° C. for 6 hours. After completion of the reaction, the temperature is cooled to around 80 ° C., the contents are taken out, and the catalyst component is filtered and separated at 70 ° C. using a 1 μm filter to obtain 3.0 kg of hydride (M-PAO-400). It was.
重合温度を90℃とした以外は上記M-PAO―400の製造と同様にして、軽質成分を取除いた無色透明の粘性液体24.2kgを得た後、炭素数20以下成分を完全に取除いた無色透明の粘性液体4.7kgを得て、さらに水素化物(M-PAO―1200)3.0キログラムを得た。 M-PAO-1200
Except for the polymerization temperature of 90 ° C., in the same manner as in the production of M-PAO-400, after obtaining 24.2 kg of a colorless and transparent viscous liquid from which light components were removed, components having 20 or less carbon atoms were completely removed. 4.7 kg of a colorless and transparent viscous liquid was removed, and 3.0 kg of hydride (M-PAO-1200) was obtained.
(1)表1に示す量の、PAO-30[又はM-PAO-30、M-PAO-45]、12-ヒドロキシステアリン酸、アゼライン酸および防錆剤を反応釜中で、撹拌しながら95℃に加熱した。
(2)水酸化リチウム(1水和物)を、その5倍量(質量比)の水に溶解させた。この水溶液を(1)の溶液に添加し、加熱混合した。混合物の温度が195℃に達した後、5分間保持した。
(3)次に、残りの基油(M-PAO-1200あるいはM-PAO-400、又はオレフィンオリゴマー)を添加した後、50℃/時間で80℃まで冷却し、表2に示した量の酸化防止剤、極圧剤を添加混合した。
(4)さらに、室温まで自然放冷した後、3本ロール装置を用いて仕上げ処理を行って実施例1~5及び比較例1のグリース組成物を得た。 Examples 1 to 5 and Comparative Example 1
(1) PAO-30 [or M-PAO-30, M-PAO-45], 12-hydroxystearic acid, azelaic acid and an antirust agent in the amounts shown in Table 1 were stirred in a reaction kettle. Heated to ° C.
(2) Lithium hydroxide (monohydrate) was dissolved in 5 times the amount (mass ratio) of water. This aqueous solution was added to the solution of (1) and mixed by heating. After the temperature of the mixture reached 195 ° C., it was held for 5 minutes.
(3) Next, the remaining base oil (M-PAO-1200 or M-PAO-400, or olefin oligomer) was added, and then cooled to 80 ° C. at 50 ° C./hour. Antioxidant and extreme pressure agent were added and mixed.
(4) Further, after naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Examples 1 to 5 and Comparative Example 1.
(1)表2に示す基油のうちその一部(出来上がりグリース量に対し50質量%分)及び、表2に示す量の12-ヒドロキシステアリン酸、アゼライン酸および防錆剤を反応釜中で、撹拌しながら95℃に加熱した。
(2)水酸化リチウム(1水和物)を、その5倍量(質量比)の水に溶解させた。この水溶液を(1)の溶液に添加し、加熱混合した。混合物の温度が195℃に達した後、5分間保持した。
(3)次に、残りの基油を添加した後、50℃/時間で80℃まで冷却し、表1に示した量の酸化防止剤、極圧剤を添加混合した。
(4)さらに、室温まで自然放冷した後、3本ロール装置を用いて仕上げ処理を行って比較例2~4のグリース組成物を得た。 Comparative Examples 2-4
(1) A part of the base oil shown in Table 2 (50% by mass with respect to the finished grease amount) and the amounts of 12-hydroxystearic acid, azelaic acid and rust inhibitor shown in Table 2 in the reaction kettle. And heated to 95 ° C. with stirring.
(2) Lithium hydroxide (monohydrate) was dissolved in 5 times the amount (mass ratio) of water. This aqueous solution was added to the solution of (1) and mixed by heating. After the temperature of the mixture reached 195 ° C., it was held for 5 minutes.
(3) Next, after the remaining base oil was added, it was cooled to 80 ° C. at 50 ° C./hour, and the amounts of antioxidant and extreme pressure agent shown in Table 1 were added and mixed.
(4) Further, after naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Comparative Examples 2 to 4.
(1)1モルのジフェニルメタン-4,4'-ジイソシアネート(MDI)を、基油全量の2/3質量に加熱溶解し、原料1とした。
(2)また、残りの基油に、2モルのシクロヘキシルアミンを撹搾溶解し、原料2とした。
(3)次に、グリース反応釜中で原料1を50~60℃で激しく撹拝しながら、原料2を除々に投入した。
撹拝しながら加熱し、グリース組成物の温度が165℃に達した後、1時間保持した。
(4)その後、50℃/時間で80℃まで冷却し、表1に示した量の酸化防止剤、極圧剤を添加混合した。室温まで自然放冷した後、3本ロール装置を用いて仕上げ処理を行って実施例6及び比較例5のグリース組成物を得た。
実施例1~6及び比較例1~5の各々で得られたグリース組成物について、下記の性状を評価した。結果を表2に示す。 Example 6 and Comparative Example 5
(1) 1 mol of diphenylmethane-4,4′-diisocyanate (MDI) was heated and dissolved to 2/3 mass of the total amount of the base oil to obtain raw material 1.
(2) Further, 2 mol of cyclohexylamine was stirred and dissolved in the remaining base oil to obtain
(3) Next, the
The mixture was heated while stirring, and held for 1 hour after the temperature of the grease composition reached 165 ° C.
(4) Thereafter, the mixture was cooled to 80 ° C. at 50 ° C./hour, and the amounts of antioxidant and extreme pressure agent shown in Table 1 were added and mixed. After naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Example 6 and Comparative Example 5.
The following properties of the grease compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated. The results are shown in Table 2.
具体的な評価方法を以下に示す。
(1)動粘度:JIS K 2283に規定される方法で測定した。
(2)混和ちょう度:JIS K 2220.7に規定される方法で測定した(25℃,60W)。
(3)滴点:JIS K 2220.8に規定される方法で測定した。
(4)フレッチング摩耗試験:ASTM D4170に規定される方法で測定した。(22±2℃)に制御した試験室に設置し試験開始後の温度制御は行わなかった。 [Evaluation methods]
A specific evaluation method is shown below.
(1) Kinematic viscosity: It was measured by the method prescribed in JIS K 2283.
(2) Mixing penetration: Measured by the method defined in JIS K 2220.7 (25 ° C., 60 W).
(3) Dropping point: Measured by the method defined in JIS K 2220.8.
(4) Fretting wear test: Measured by the method defined in ASTM D4170. It was installed in a test room controlled at (22 ± 2 ° C.) and temperature control after the start of the test was not performed.
玉の数を3個に減らした呼び番号51103のスラスト玉軸受(日本精工(株)製)に対し、0.01~0.69kNのスラスト荷重を10Hzの周期で与える。
22±2℃にコントロールした室内で8時間の試験を行なった。試験後の軸受について、楕円状にみえる摩耗痕について観察し、下記のように評価した。
×:明確な摩耗が認められる。摩耗痕が楕円の全集に渡り、ドーナツ状になっている。
△:明確な摩耗が認められる。
○:圧痕のみ観察される、又は摩耗が認められない。 (5) Fretting wear test (Thrust load fluctuation method)
A thrust load of 0.01 to 0.69 kN is applied at a cycle of 10 Hz to a thrust ball bearing (Nippon Seiko Co., Ltd.) having a nominal number 51103 in which the number of balls is reduced to three.
The test was conducted for 8 hours in a room controlled at 22 ± 2 ° C. The bearings after the test were observed for wear marks that looked oval and evaluated as follows.
X: Clear wear is recognized. The wear marks are donut-shaped over the entire collection of ellipses.
Δ: Clear wear is observed.
○: Only indentation is observed or no wear is observed.
(7)高荷重軸受摩耗試験:DIN51819-2に規定された方法で測定した。
(試験条件 DIN51819-2-C-75/50-120, 荷重50KN,温度120℃、回転数75rpm)軌道輪(内輪+外輪)、転動体(コロ16個の合計)、保持器の重量を試験前後で測定し、軸受1個あたりのそれぞれの重量減をDIN51819-2.11に規定される50%摩耗確率(50%probability of wear)として求めた。 (6) Low temperature torque test: Measured by the method defined in JIS K 2220.18. The temperature was −40 ° C.
(7) High-load bearing wear test: Measured by the method specified in DIN51819-2.
(Test conditions DIN51819-2-C-75 / 50-120, load 50KN, temperature 120 ° C, rotation speed 75rpm) Test the weight of the bearing ring (inner ring + outer ring), rolling elements (total of 16 rollers), and cage Measured before and after, the respective weight loss per bearing was determined as 50% probability of wear as defined in DIN 51819-2.11.
(9)グリース圧送性:グリースの自動給脂ポンプを用いてグリースを押しだす際の吐出圧力で評価した。自動給脂ポンプ(LINCOLN INDUSTRIAL社製、Quicklub Pump model 203)のグリース吐出口に、圧力計(吐出圧力測定用)、内径4mmの配管(10m)の順に接続し、更に分配弁を用いて2系統に分配する。それぞれの系統に、内径4mm×長さ4mの配管を接続し、更にリリーフ弁(12MPa)を経由してグリースは排出される。20~25℃にコントロールした室内で、グリースをポンプ・配管内に満たし、吐出圧が安定してから2時間ポンプを運転し、この間の平均吐出圧力(MPa)を計測した。吐出圧力が小さいグリースほど、小さい圧力で押し出すことが出来るため、圧送性に優れる。 (8) Degree of oil separation under pressure: measured by the method defined in IP121 (40 ° C., 42 h).
(9) Grease pumpability: Evaluated by the discharge pressure when the grease was pushed out using an automatic grease feed pump. Connect a grease gauge to the grease discharge port of an automatic greasing pump (manufactured by LINCOLN INDUSTRIAL, Quicklub Pump model 203) in the order of a pressure gauge (for discharge pressure measurement) and a pipe with an inner diameter of 4 mm (10 m). To distribute. Pipes with an inner diameter of 4 mm and a length of 4 m are connected to each system, and the grease is discharged via a relief valve (12 MPa). In a room controlled at 20 to 25 ° C., grease was filled in the pump and piping, the pump was operated for 2 hours after the discharge pressure was stabilized, and the average discharge pressure (MPa) during this period was measured. A grease with a lower discharge pressure can be pushed out with a lower pressure, and therefore has better pumpability.
表2の結果から明らかなように、実施例1~6のグリース組成物は、いずれも軸受摩耗特性及びフレッチング摩耗特性、さらには低温性能、圧送性に優れていることがわかる。特に実施例3、6では、低温トルク性にも優れることがわかり、屋外に設置される風力発電装置などにも好適に使用できることがわかる。一方、比較例1~5では、高粘度A成分を含有しないため、揺動方向への微小振動に伴うフレッチング摩耗の低減と、スラスト方向の荷重変動に伴うフレッチング摩耗の低減の両立を図ることができず、また、軸受特性も劣る。 [Evaluation results]
As is apparent from the results in Table 2, it can be seen that the grease compositions of Examples 1 to 6 are all excellent in bearing wear characteristics and fretting wear characteristics, as well as low temperature performance and pumpability. In particular, in Examples 3 and 6, it can be seen that the low-temperature torque property is excellent, and it can be suitably used for a wind power generator installed outdoors. On the other hand, Comparative Examples 1 to 5 do not contain a high-viscosity A component, so it is possible to reduce both fretting wear associated with minute vibrations in the swing direction and fretting wear associated with load fluctuations in the thrust direction. In addition, the bearing characteristics are inferior.
Claims (10)
- 基油及び増ちょう剤を含むグリース組成物であって、前記基油が、40℃における動粘度が300mm2/s以上の、メタロセン触媒を用いて製造されたポリ-α-オレフィン(A成分)を含有するグリース組成物。 A grease composition comprising a base oil and a thickener, wherein the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a metallocene catalyst (component A) Containing a grease composition.
- 前記A成分の40℃における動粘度が600mm2/s以上である、請求項1記載のグリース組成物。 The grease composition according to claim 1, wherein the kinematic viscosity of the component A at 40 ° C. is 600 mm 2 / s or more.
- 前記A成分を、組成物全量基準で20質量%以上含有する、請求項1または2に記載のグリース組成物。 The grease composition according to claim 1 or 2, wherein the component A contains 20% by mass or more based on the total amount of the composition.
- 前記基油の40℃における動粘度が150~2000mm2/sであって、混和ちょう度が220~385である、請求項1~3のいずれか1項に記載のグリース組成物。 The grease composition according to any one of claims 1 to 3, wherein the base oil has a kinematic viscosity at 40 ° C of 150 to 2000 mm 2 / s and a penetration of 220 to 385.
- 前記基油が、40℃における動粘度が70mm2/s以下であるB成分を、組成物全量基準で10~70質量%含有する、請求項1~4のいずれか1項に記載のグリース組成物。 The grease composition according to any one of claims 1 to 4, wherein the base oil contains 10 to 70% by mass of a B component having a kinematic viscosity at 40 ° C of 70 mm 2 / s or less based on the total amount of the composition. object.
- 前記増ちょう剤を、組成物全量基準で17質量%以下含有する、請求項1~5のいずれか1項に記載のグリース組成物。 6. The grease composition according to claim 1, wherein the thickener is contained in an amount of 17% by mass or less based on the total amount of the composition.
- 前記増ちょう剤が石けん系増ちょう剤である、請求項1~6のいずれか1項に記載のグリース組成物。 The grease composition according to any one of claims 1 to 6, wherein the thickener is a soap-type thickener.
- 前記増ちょう剤が、前記B成分中にてカルボン酸とアルカリとの反応を行うことにより製造された、請求項1~7のいずれか1項に記載のグリース組成物。 The grease composition according to any one of claims 1 to 7, wherein the thickener is produced by reacting a carboxylic acid and an alkali in the component B.
- 硫黄を含む極圧添加剤が組成物全量基準で0.01~10質量%配合されている、請求項1~8のいずれか1項に記載のグリース組成物。 The grease composition according to any one of claims 1 to 8, wherein an extreme pressure additive containing sulfur is blended in an amount of 0.01 to 10% by mass based on the total amount of the composition.
- 風力発電装置に使用されるグリース組成物であって、該風力発電装置の羽が連結された主軸に連接されたメインベアリング、及び、前記羽に組み込まれた羽軸に連接されたピッチベアリングのうち少なくとも一方に使用される、請求項1~9のいずれか1項に記載のグリース組成物。 A grease composition used for a wind power generator, comprising: a main bearing connected to a main shaft to which a wing of the wind power generator is connected; and a pitch bearing connected to a wing shaft incorporated in the wing. The grease composition according to any one of claims 1 to 9, which is used in at least one of them.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012507118A JP5706883B2 (en) | 2010-03-26 | 2011-03-25 | Grease composition |
US13/636,940 US20130012416A1 (en) | 2010-03-26 | 2011-03-25 | Grease composition |
CN2011800137827A CN102791841A (en) | 2010-03-26 | 2011-03-25 | Grease composition |
EP11759618.9A EP2554644A4 (en) | 2010-03-26 | 2011-03-25 | Grease composition |
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JP2010-073663 | 2010-03-26 |
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WO2011118814A1 true WO2011118814A1 (en) | 2011-09-29 |
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PCT/JP2011/057462 WO2011118814A1 (en) | 2010-03-26 | 2011-03-25 | Grease composition |
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US (1) | US20130012416A1 (en) |
EP (1) | EP2554644A4 (en) |
JP (1) | JP5706883B2 (en) |
CN (1) | CN102791841A (en) |
WO (1) | WO2011118814A1 (en) |
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JPWO2019131437A1 (en) * | 2017-12-27 | 2020-12-10 | 出光興産株式会社 | Grease composition and how to use the grease composition |
JPWO2019189239A1 (en) * | 2018-03-30 | 2021-04-01 | 出光興産株式会社 | Grease composition, mechanical parts, and method for manufacturing grease composition |
JP2021161297A (en) * | 2020-03-31 | 2021-10-11 | 出光興産株式会社 | Grease composition |
JP2021187911A (en) * | 2020-05-27 | 2021-12-13 | コスモ石油ルブリカンツ株式会社 | Lubricating oil composition |
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CN110157525A (en) * | 2019-06-13 | 2019-08-23 | 安徽和欣润滑科技有限公司 | A kind of composition and preparation method of motor turning stacked switch lubricating grease |
CN113684084A (en) * | 2021-09-15 | 2021-11-23 | 陈伟民 | Functional lubricating oil and preparation method thereof |
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JPWO2019131437A1 (en) * | 2017-12-27 | 2020-12-10 | 出光興産株式会社 | Grease composition and how to use the grease composition |
JP7108636B2 (en) | 2017-12-27 | 2022-07-28 | 出光興産株式会社 | Grease composition and method of using grease composition |
JPWO2019189239A1 (en) * | 2018-03-30 | 2021-04-01 | 出光興産株式会社 | Grease composition, mechanical parts, and method for manufacturing grease composition |
US11542453B2 (en) | 2018-03-30 | 2023-01-03 | Idemitsu Kosan Co., Ltd. | Grease composition, mechanism component, and production method for grease composition |
JP7235728B2 (en) | 2018-03-30 | 2023-03-08 | 出光興産株式会社 | Grease composition, mechanism part, and method for producing grease composition |
JP2021161297A (en) * | 2020-03-31 | 2021-10-11 | 出光興産株式会社 | Grease composition |
JP7341940B2 (en) | 2020-03-31 | 2023-09-11 | 出光興産株式会社 | grease composition |
JP2021187911A (en) * | 2020-05-27 | 2021-12-13 | コスモ石油ルブリカンツ株式会社 | Lubricating oil composition |
JP7460445B2 (en) | 2020-05-27 | 2024-04-02 | コスモ石油ルブリカンツ株式会社 | Lubricating Oil Composition |
Also Published As
Publication number | Publication date |
---|---|
EP2554644A4 (en) | 2013-12-04 |
US20130012416A1 (en) | 2013-01-10 |
JPWO2011118814A1 (en) | 2013-07-04 |
JP5706883B2 (en) | 2015-04-22 |
CN102791841A (en) | 2012-11-21 |
EP2554644A1 (en) | 2013-02-06 |
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