WO2011046079A1 - Lubricating grease composition for reciprocating sliding, and manufacturing method therefor - Google Patents

Lubricating grease composition for reciprocating sliding, and manufacturing method therefor Download PDF

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Publication number
WO2011046079A1
WO2011046079A1 PCT/JP2010/067744 JP2010067744W WO2011046079A1 WO 2011046079 A1 WO2011046079 A1 WO 2011046079A1 JP 2010067744 W JP2010067744 W JP 2010067744W WO 2011046079 A1 WO2011046079 A1 WO 2011046079A1
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Prior art keywords
base oil
fluorinated
weight
lubricating grease
grease composition
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PCT/JP2010/067744
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French (fr)
Japanese (ja)
Inventor
幸 橋田
英徳 若松
泰広 岡本
敏夫 新田
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Ｎｏｋクリューバー株式会社
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Priority to JP2011511173A priority Critical patent/JP5429285B2/en
Publication of WO2011046079A1 publication Critical patent/WO2011046079A1/en

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1256—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 used as thickening agent
    • 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
    • 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
    • C10M2207/127—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 polycarboxylic
    • C10M2207/1276—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 polycarboxylic used as thickening agent
    • 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
    • C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
    • C10M2229/0515—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • 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 lubricating grease composition for reciprocating sliding and a method for producing the same. More specifically, the present invention relates to a lubricating grease composition for reciprocating sliding using a base oil mixture comprising a non-fluorinated base oil and a fluorine-based base oil, which are incompatible with each other, and a method for producing the same.
  • an enclosed microswitch is a component that transmits an external force applied to an actuator portion to an internal spring mechanism to move a movable contact to open and close the switch.
  • the external force applied to the actuator is replaced by the reciprocating movement of the plunger for opening and closing the switch.
  • the reciprocating movement with the movable range of several mm is repeated.
  • fluorine-based greases are conventionally used, and are used under severe conditions where low temperature characteristics, oxidation stability, chemical resistance, etc. are required as well as high temperature durability.
  • a fluorine-based grease is generally composed of a perfluoropolyether oil as a base oil, a homopolymer of tetrafluoroethylene [PTFE], a copolymer of tetrafluoroethylene and hexafluoropropene [HFP], etc. as a thickener. It is done.
  • PTFE tetrafluoroethylene
  • HFP hexafluoropropene
  • the grease interposed between the balls and the transfer surface not only contributes to lubrication but also exists in the peripheral portion not contributing to sliding.
  • Grease is also able to contribute to lubrication later by moving in the bearing by rotational movement and being supplied to the sliding part, so there is no problem in this case.
  • Patent Document 1 describes a grease comprising hydrogenated mineral oil and / or synthetic lubricating oil, fluoropolyether and thickener used at a specific mixing ratio, ester oil, 12-hydroxystearic acid
  • a grease obtained by adding perfluorinated oil and PTFE to a grease consisting of azelaic acid and lithium hydroxide is shown as Example 4, but its evaluation test is about sticking temperature, weight loss due to evaporation, oil separation Only the bearing high temperature life is not evaluated, and no specific description of its application is found.
  • Patent Document 2 describes a lubricating grease composition containing a perfluoropolyether oil, a synthetic lubricating oil and a thickener, the evaluation of which is low temperature torque, rotational life, wear scar diameter (shell abrasion test) About is done.
  • Patent Document 3 describes a lubricating grease composition containing a fluorinated oil and a lithium-based composite soap thickener in a base oil comprising a synthetic hydrocarbon oil, an ester oil or an ether-based synthetic oil, The evaluation is conducted for the pin on disk wear test.
  • Patent Document 4 as a lubricating grease composition excellent in extreme pressure property and wear resistance, a composition is prepared by mixing a perfluoropolyether base oil with a fatty acid metal salt and a fluorine resin as a thickener.
  • An object of the present invention is a lubricating grease composition for reciprocating sliding, in which a thickener and a fluorine resin are contained in a base oil mixture consisting of a non-fluorinated base oil and a fluorinated base oil, which is necessary for lubricating greases for reciprocating sliding.
  • the object of the present invention is non-fluorine having a dropping point of 250 ° C. or more, wherein a non-fluorinated base oil contains a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid or aliphatic monocarboxylic acid.
  • a lubricating grease composition for reciprocating sliding comprising a mixture of two greases of a fluorocarbon resin and a fluorocarbon base oil incompatible with a non-fluorocarbon base oil and a fluorocarbon oil.
  • a non-fluorinated base oil comprising two grease mixtures of a non-fluorinated grease in which a composite metal soap thickener is contained in a non-fluorinated base oil and a fluorine-based grease in which a fluorocarbon powder is contained in a fluorinated base oil.
  • Evaporative loss and oil separation are small by using a non-fluorinated grease containing complex metal soap in it and having a dropping point corresponding to the upper limit temperature established as grease, at 250 ° C. or higher, and the SRV test ( A stable lubricating grease composition is obtained which has a small fluctuation range of the friction coefficient in the reciprocation test and a small fluctuation thereof.
  • a base oil mixture composed of a non-fluorinated base oil and a fluorinated base oil which are incompatible with each other even under conditions where the fluorine-based grease is difficult to be sufficiently held in the sliding portion and difficult to be supplied.
  • a lubricating grease composition containing a metal complex soap thickener and a fluorocarbon resin powder, and using a metal complex soap-containing non-fluorine base oil (non-fluorine grease) having a dropping point of a predetermined temperature or more
  • non-fluorinated base oil and the fluorinated base oil which are base oil mixtures used in the present invention those which are not compatible with each other are used. Incompatibility with one another means that a simple base oil mixture can not be formed when the two are simply mixed.
  • Non-fluorinated base oils include, for example, poly- ⁇ -olefins, ethylene- ⁇ -olefin oligomers, polybutenes or their hydrides, synthetic hydrocarbon oils such as alkylbenzenes and alkylnaphthalenes, polyalkylene glycols, polyphenyl ethers, alkyl substituted Synthetic ethers of ethers such as diphenyl ether, aromatic polyvalent carboxylic acid esters such as trimellitic acid ester, pyromellitic acid ester, neopentyl glycol ester, trimethylol propane ester, pentaerythritol ester, polyol ester such as dipentaerythritol ester, Furthermore, ester-based synthetic oils such as aliphatic dibasic acid esters, phosphoric acid esters, phosphites and carbonic esters, paraffinic mineral oils, naphthenic mineral oils, and mineral oils obtained by refining these. Also one
  • kinematic viscosity at 40 ° C. in accordance with JIS K 2283 corresponding to ASTM D445
  • a kinematic viscosity at 40 ° C. in accordance with JIS K 2283 corresponding to ASTM D445
  • the high temperature durability is poor, that is, the evaporation amount is large
  • the kinematic viscosity is more than this, the permeability to the gap at the sliding becomes worse, and grease breakage tends to occur.
  • a kinematic viscosity at 40 ° C. in accordance with JIS K 2283 corresponding to ASTM D445
  • the fluorine-based base oil for the same reason as the case of the non-fluorine-based base oil, kinematic viscosity at 40 ° C. (JIS K2283 compliant) is about 15 ⁇ 350 mm 2 / sec, it is preferably of about 20 ⁇ 300 mm 2 / s commonly used, and more specifically the general formula RfO (CF 2 O) x ( C 2 F 4 O) y (C 3 F 6 O) z Rf
  • the one represented by is used. Specifically, for example, those represented by the following general formulas (1) to (4) are used, and those represented by the other general formula (5) are also used.
  • Rf is a perfluoro lower alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, such as perfluoromethyl group, perfluoroethyl group, perfluoropropyl group and the like.
  • m + n 3 to 200
  • m: n 10 to 90: 90 to 10
  • CF 2 CF 2 O and CF 2 O are randomly bonded in the main chain. It is obtained by completely fluorinating a precursor produced by photooxidation polymerization of tetrafluoroethylene.
  • the non-fluorinated base oil and the fluorinated base oil are generally composed of 1 to 95% by weight, preferably 6 to 89% by weight of the former, and 99 to 5% by weight, preferably 94 to 11% by weight of the latter. Used in proportions. If the mixing ratio of the non-fluorinated base oil is less than this, the load resistance improves, but the wear resistance, heat resistance, shear stability, etc. become inferior, while if the mixing ratio is more than this, the wear resistance It becomes poor in heat resistance, load resistance, shear stability, etc.
  • Complex metal soaps as thickeners are formed as complex metal soaps of aliphatic dicarboxylic acids and monoamide monocarboxylic acids or aliphatic monocarboxylic acids. The formation of the complex metal soap is carried out during the preparation of the lubricating grease composition as described below.
  • saturated dicarboxylic acid saturated or unsaturated dicarboxylic acid having 2 to 20 carbon atoms is used.
  • saturated dicarboxylic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid, undecanedicarboxylic acid And dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid and the like, and preferably adipic acid, pimelic acid, suberic acid, azelaic acid, sebacine Acid
  • unsaturated dicarboxylic acid for example, maleic acid, fumaric acid, and further alkenyl succinic acid such as 2-methylene succinic acid, 2-ethylene succinic acid, 2-methylene glutaric acid and the like are used. These saturated or unsaturated dicarboxylic acids may be used alone or in combination of two or more.
  • the monoamide monocarboxylic acid is obtained by amidating the monocarboxylic group of the above dicarboxylic acid, and as the amine to be amidated, for example, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine
  • Aliphatic primary amines such as myristylamine, palmitylamine, stearylamine, behenylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dilaurylamine, monomethyllaurylamine, distearylamine, monomethylstearylamine, Aliphatic secondary amines such as dimyristylamine and dipalmitylamine, aliphatic unsaturated amines such as allylamine, diallylamine, oleylamine and dioleylamine, cyclopropyl And cycloaliphatic amines such
  • aliphatic monocarboxylic acids for example, saturated fatty acids such as butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid or the like
  • unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and ricinolenic acid are used, preferably 12-hydroxystearic acid.
  • aliphatic dicarboxylic acids and monoamide monocarboxylic acids or aliphatic monocarboxylic acids are used at a molar ratio of 0.1 to 10, preferably 0.5 to 5, with respect to the former. When it is used at a mixing ratio other than this, the dropping point is lowered, which is not preferable. Both of them are used in the form of complex metal soap with metal compounds such as lithium, sodium, potassium, calcium, barium, magnesium, copper, iron, cobalt, zinc and aluminum used in the form of hydroxides and oxides. Preferably, it is used as a complex barium soap or a complex lithium soap.
  • the metal compound used to prepare the complex metal soap is used in an amount approximately equivalent to the theoretical amount required for the saponification reaction.
  • fluorocarbon resin powder PTFE powder, HFP powder, perfluoroalkylene resin powder or the like is used.
  • fluorine resin powders having an average primary particle size of about 500 ⁇ m or less, preferably about 0.1 to 30 ⁇ m, are used.
  • PTFE polytetrafluoroethylene manufactures polytetrafluoroethylene by methods such as emulsion polymerization, suspension polymerization, solution polymerization and the like of tetrafluoroethylene, and methods such as thermal decomposition, electron beam irradiation decomposition, physical pulverization and the like And those having a number average molecular weight Mn of about 1000 to 1,000,000 are used. Further, in the case of HFP powder, the copolymerization reaction of tetrafluoroethylene and hexafluoropropene and the molecular weight reduction treatment are also carried out in the same manner as in the case of polytetrafluoroethylene, and the number average molecular weight Mn is about 1000 to 600000. The degree is used. The control of the molecular weight can also be carried out by using a chain transfer agent at the time of the copolymerization reaction.
  • non-fluorinated grease which is a non-fluorinated base oil containing a complex metal soap thickener
  • grease (fluorinated grease) which is a fluorinated base oil containing fluorine resin powder.
  • the lubricating grease composition of the invention is prepared.
  • the formation of the complex metal soap and the preparation of the lubricating grease composition are carried out as follows.
  • (a-1) A non-fluorinated base oil, an aliphatic dicarboxylic acid and a monoamide monocarboxylic acid or an aliphatic monocarboxylic acid are added to a reaction vessel capable of heating and stirring, and the temperature is such that stirring is possible, and the reaction is efficiently performed.
  • Advanced and heated to about 80-180 ° C., which is a temperature that does not cause deterioration of the base oil, and stirred, to which a metal hydroxide or metal oxide is added to form a composite metal soap in a non-fluorinated base oil .
  • a non-fluorinated base oil is blended therein, for example, in a proportion to occupy about 0.1 to 5% by weight in a non-fluorinated base oil, and it is kneaded using a triple roll mill or a high pressure homogenizer to obtain non-fluorine.
  • a grease system It is also possible to add and use other non-fluorinated base oils other than the first used non-fluorinated base oil prior to kneading.
  • a-2 The fluorinated base oil and the fluorocarbon resin powder are mixed in a mixing pot, and thereafter, they are kneaded using a three-roll mill or a high pressure homogenizer to prepare a fluorinated grease.
  • a fluorine-based base oil and a fluorine resin are added to the non-fluorinated grease prepared as described above, and they are mixed in a mixing kettle and then kneaded using a triple roll mill or a high pressure homogenizer.
  • Lubricating grease compositions can also be prepared.
  • the grease which is a non-fluorinated base oil containing a complex metal soap thickener
  • one having a dropping point of 250 ° C. or higher corresponding to the upper limit temperature established as a grease is used.
  • a non-fluorinated grease having a dropping point of less than 250 ° C. there may be a problem of reduced product reliability when applied to reciprocating sliding applications at temperatures of 120 to 150 ° C. or more.
  • the dropping point is measured in accordance with JIS K 2220.8 corresponding to ISO 2176.
  • the non-fluorinated base oil is used in a proportion of 1 to 90% by weight, preferably 5 to 80% by weight, with the non-fluorinated base oil in the mixing ratio as described above
  • the content of the fluorinated base oil is 5 to 80% by weight, preferably 10 to 80% by weight
  • the complex metal soap is 0.5 to 30% by weight, preferably 1 to 25% by weight
  • the fluorocarbon resin powder is 0.1 to It is used in a proportion of 20% by weight, preferably 1 to 15% by weight.
  • antioxidants used in conventional lubricants, such as antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure agents, oil agents, solid lubricants, etc. are further incorporated as necessary. be able to.
  • antioxidants for example, phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis (2,6-di-tert-butylphenol), C 4 -C Amine-based antioxidants such as alkyldiphenylamines having 20 alkyl groups, triphenylamines, phenyl- ⁇ -naphthylamines, alkylated phenyl- ⁇ -naphthylamines, phenothiazines, alkylated phenothiazines, and further phosphorus-based antioxidants, sulfur And antioxidants and the like.
  • antirust agent examples include fatty acids, fatty acid metal salts, fatty acid amines, alkylsulfonic acid metal salts, alkylsulfonic acid amine salts, oxidized paraffins, oxidized paraffins, polyoxyethylene alkyl ethers and the like, and corrosion inhibitors include, for example, benzo Triazole, benzimidazole, thiadiazole and the like can be mentioned.
  • phosphorus compounds such as phosphoric acid ester, phosphorous acid ester, phosphoric acid ester amine salt, sulfur compounds such as sulfides and disulfides, metal salts of dialkyl dithiophosphates, metal salts of dialkyl dithiocarbamates, etc.
  • sulfur-based compound metal salts chlorinated paraffins, chlorinated compounds such as chlorinated diphenyl, and the like.
  • oil agent examples include fatty acids or esters thereof, higher alcohols, polyhydric alcohols or esters thereof, aliphatic esters, aliphatic amines, fatty acid monoglycerides, montan waxes, amide waxes and the like.
  • solid lubricant for example, molybdenum disulfide, graphite, boron nitride, silane nitride, melamine cyanurate and the like can be mentioned.
  • those having an average primary particle size of 30 ⁇ m or less, preferably 0.1 to 20 ⁇ m are used.
  • thickeners generally and conventionally used as thickeners, such as silica, clay, graphite, zinc oxide, urea compounds, polyethylene, polypropylene, polyamide, organic pigments, metal soaps and the like are appropriately added. It can also be used.
  • Reference Example 3 A method as described above (a-) of a barium complex soap of azelaic acid and azelaic acid monooctylamide, which comprises 25% by weight of a nonfluorinated grease as a thickener, in alkyl naphthalene (40 ° C. viscosity: 114 mm 2 / s) After synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, the mixture was kneaded twice with a three-roll mill to prepare grease C. The dropping point of the obtained grease C was 273 ° C.
  • Reference Example 4 A method as described above (a-) of a barium complex soap of sebacic acid and sebacic acid monostearylamide which accounts for 15% by weight in non-fluorinated grease as a thickener in diphenyl ether oil (40 ° C. viscosity: 100 mm 2 / s) After synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, the mixture was kneaded twice with a three-roll mill to prepare grease D. The dropping point of the obtained grease D was 262 ° C.
  • Reference Example 5 A method as described above (a-) of a barium complex soap of sebacic acid and sebacic acid monostearylamide which accounts for 25% by weight in non-fluorinated grease as a thickener in diphenyl ether oil (40 ° C. viscosity: 100 mm 2 / s) After synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, the mixture was kneaded twice with a three-roll mill to prepare grease E. The dropping point of the obtained grease E was 270 ° C.
  • Reference Example 6 Lithium complex soap of azelaic acid and 12-hydroxystearic acid in poly- ⁇ -olefin oil (40 ° C. viscosity: 46 mm 2 / s), accounting for 20% by weight in non-fluorinated grease as thickener in the above-mentioned (A-1), 2 wt% of an amine antioxidant (NA-LUBE AO-120) was added thereto, and the mixture was kneaded twice with a three-roll mill to prepare grease F. . The dropping point of the obtained grease F was 280 ° C.
  • Reference Example 7 A method as described above (a-) a lithium complex soap of sebacic acid and 12-hydroxystearic acid which accounts for 20% by weight in non-fluorinated grease as a thickener in diphenyl ether oil (40 ° C. viscosity: 100 mm 2 / s)
  • a grease G was prepared by synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, followed by kneading twice with a three-roll mill. The dropping point of the obtained grease G was 269 ° C.
  • Reference Example 8 Synthesized lithium soap of 12-hydroxystearic acid in poly- ⁇ -olefin oil (40 ° C viscosity: 30 mm 2 / s) and accounting for 10% by weight in non-fluorinated grease as thickener, 2 weight on this % Grease was added thereto, and then the mixture was kneaded twice with a three-roll mill to prepare grease H. The dropping point of the obtained grease H was 182 ° C.
  • Reference Example 10 PTFE powder (average particles) in an amount of 27% by weight in a fluorine-based grease in a base oil (40 ° C. viscosity: 85 mm 2 / s) having a molecular structure RfO (CF 2 CF 2 O) m (CF 2 O) n Rf Grease II was prepared by mixing 0.3 ⁇ m in diameter and kneading twice with a three-roll mill. The dropping point of the obtained grease II was 300 ° C. or more.
  • Reference Example 11 PTFE powder (average particles) in an amount of 15% by weight in a fluorine-based grease in a base oil (40 ° C. viscosity: 85 mm 2 / s) having a molecular structure RfO (CF 2 CF 2 O) m (CF 2 O) n Rf Grease III was prepared by mixing 0.3 ⁇ m in diameter and kneading twice with a three-roll mill. The dropping point of the obtained grease III was 300 ° C. or more.
  • Reference Example 12 PTFE powder (average amount of 31% by weight of fluorine-based grease in base oil having a molecular structure F (CF 2 CF 2 CF 2 O) 2 to 100 C 2 F 5 (40 ° C. viscosity: 65 mm 2 / sec)
  • the particle size was 0.3 ⁇ m, and the mixture was kneaded twice with a three-roll mill to prepare Grease IV.
  • the dropping point of the obtained grease IV was 300 ° C. or more.
  • Evaporative loss heat resistance
  • Oil separation degree heat resistance
  • the lubricating grease composition according to the present invention is used as a lubricating grease for reciprocating sliding, for example, for actuator parts such as micro switches and electromagnetically driven valves used under high temperature conditions of 120 to 150 ° C. or more.
  • actuator parts such as micro switches and electromagnetically driven valves used under high temperature conditions of 120 to 150 ° C. or more.
  • parts such as a guide rail, a slide rail, a piston, a cam mechanism, etc. that act as lubricating grease for reciprocating sliding.

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Abstract

Provided is a lubricating grease composition for reciprocating sliding. Said grease composition comprises a mixture of two types of grease: a grease that has a dropping point of at least 250°C and contains, in a non-fluorine base oil, either an aliphatic dicarboxylic acid and a monoamide monocarboxylic acid or a composite metal soap thickener with an aliphatic monocarboxylic acid; and a grease that contains a fluorine resin powder in a fluorine base oil that is not compatible with the non-fluorine base oil. The provided lubricating grease composition, which contains a thickener and a fluorine resin in a base oil mixture comprising a non-fluorine base oil and a fluorine base oil, has the properties necessary for a lubricating grease composition for reciprocating sliding.

Description

往復摺動用潤滑グリース組成物およびその製造法Lubricating grease composition for reciprocating sliding and method for producing the same
　本発明は、往復摺動用潤滑グリース組成物およびその製造法に関する。さらに詳しくは、互いに相溶性のない非フッ素系基油およびフッ素系基油よりなる基油混合物を用いた往復摺動用潤滑グリース組成物およびその製造法に関する。 The present invention relates to a lubricating grease composition for reciprocating sliding and a method for producing the same. More specifically, the present invention relates to a lubricating grease composition for reciprocating sliding using a base oil mixture comprising a non-fluorinated base oil and a fluorine-based base oil, which are incompatible with each other, and a method for producing the same.
　往復摺動機構を有する代表的な産業用小型部品としては、マイクロスイッチや電磁駆動弁等がある。例えば、封入形マイクロスイッチは、アクチュエータ部位に加えられた外力が、内部のバネ機構に伝わり、可動接点を動かし、スイッチの開閉を行わせる部品である。アクチュエータに加えられた外力は、スイッチの開閉を行うためのプランジャの往復動に置き換えられる。その場合、プランジャと封入ケース部材との間の摺動は、可動範囲が数mmの往復動がくり返し行われる。 As a typical industrial small part having a reciprocating sliding mechanism, there are a micro switch, an electromagnetically driven valve and the like. For example, an enclosed microswitch is a component that transmits an external force applied to an actuator portion to an internal spring mechanism to move a movable contact to open and close the switch. The external force applied to the actuator is replaced by the reciprocating movement of the plunger for opening and closing the switch. In that case, as for the sliding between the plunger and the enclosing case member, the reciprocating movement with the movable range of several mm is repeated.
　この種の用途には、従来鉱油系や合成炭化水素油〔PAO〕系のグリースが使用されてきたが、近年は例えば120～150℃あるいはそれ以上の高温条件下において使用される封入形マイクロスイッチにおいては、グリースの耐久性が不足するという問題が発生している。 Mineral oil-based and synthetic hydrocarbon oil (PAO) -based greases have conventionally been used for this type of application, but in recent years, encapsulated microswitches used under high temperature conditions of 120 to 150 ° C. or higher, for example. In the above, there is a problem that the durability of the grease is insufficient.
　高温耐久性という点では、従来からフッ素系のグリースが使用されており、高温耐久性のみならず、低温特性、酸化安定性、耐薬品性などが必要とされる苛酷な条件下で使用されている。フッ素系のグリースは、一般にパーフルオロポリエーテル油を基油として、テトラフルオロエチレンの単独重合体〔PTFE〕やテトラフルオロエチレンとヘキサフルオロプロペンとの共重合体〔HFP〕等を増稠剤として構成されている。しかしながら、これらのフッ素系グリースは、被潤滑材料である樹脂、ゴム、金属等とのなじみが悪いという欠点を有する。 In terms of high temperature durability, fluorine-based greases are conventionally used, and are used under severe conditions where low temperature characteristics, oxidation stability, chemical resistance, etc. are required as well as high temperature durability. There is. A fluorine-based grease is generally composed of a perfluoropolyether oil as a base oil, a homopolymer of tetrafluoroethylene [PTFE], a copolymer of tetrafluoroethylene and hexafluoropropene [HFP], etc. as a thickener. It is done. However, these fluorine-based greases have the disadvantage that they do not conform well to the resin to be lubricated, rubber, metal or the like.
　転がり軸受に代表される転動装置等に使用される場合には、ボールと転送面との間に介在するグリースが潤滑に寄与するばかりではなく、摺動に寄与していない周囲部分に存在するグリースも、回転運動により軸受内を移動し、摺動部に供給されることで、後々潤滑に寄与することが可能であるから、この場合には問題がみられない。 When used in rolling devices represented by rolling bearings, the grease interposed between the balls and the transfer surface not only contributes to lubrication but also exists in the peripheral portion not contributing to sliding. Grease is also able to contribute to lubrication later by moving in the bearing by rotational movement and being supplied to the sliding part, so there is no problem in this case.
　これに対し、一定間隔のくり返し摺動となる往復動では、グリースが摺動部から掻き取られ易く、また一度摺動部から掻き取られたグリースは、再度摺動部に供給され難いため、特にフッ素系グリースにあっては潤滑に必要な油膜が形成されず、その結果摩耗が発生したり、摩擦係数が高くなったりして、耐久性が得られなくなるといった問題を発生させる。 On the other hand, in the case of a reciprocating motion which is repeated sliding at a constant interval, the grease is easily scraped off from the sliding portion, and the grease scraped off once from the sliding portion is difficult to be supplied again to the sliding portion. In the case of a fluorine-based grease, in particular, an oil film necessary for lubrication is not formed, resulting in the occurrence of wear and an increase in the coefficient of friction, resulting in the problem that the durability can not be obtained.
　特許文献１には、特定の混合割合で用いられた水素添加鉱油および／または合成潤滑油、フルオロポリエーテルおよび増稠剤を含んでなるグリースが記載されており、エステル油、12-ヒドロキシステアリン酸、アゼライン酸および水酸化リチウムよりなるグリースに過フッ素化油およびPTFEを添加したグリースが、実施例４として示されているが、それの評価試験は固着温度、蒸発による重量損失、油分離性についてのみなされており、軸受高温寿命については評価されておらず、それの用途についての具体的記載はみられない。 Patent Document 1 describes a grease comprising hydrogenated mineral oil and / or synthetic lubricating oil, fluoropolyether and thickener used at a specific mixing ratio, ester oil, 12-hydroxystearic acid A grease obtained by adding perfluorinated oil and PTFE to a grease consisting of azelaic acid and lithium hydroxide is shown as Example 4, but its evaluation test is about sticking temperature, weight loss due to evaporation, oil separation Only the bearing high temperature life is not evaluated, and no specific description of its application is found.
　電気接点等の摺動部に用いられるグリースについては、本出願人自身がいくつかの提案を行っている。 The present applicant has made several proposals for grease used in sliding parts such as electrical contacts.
　特許文献２には、パーフルオロポリエーテル油、合成潤滑油および増稠剤を含有する潤滑グリース組成物が記載されており、それの評価は低温トルク、回転寿命、摩耗痕径(シェル摩耗試験)について行われている。 Patent Document 2 describes a lubricating grease composition containing a perfluoropolyether oil, a synthetic lubricating oil and a thickener, the evaluation of which is low temperature torque, rotational life, wear scar diameter (shell abrasion test) About is done.
　特許文献３には、合成炭化水素油、エステル油またはエーテル系合成油よりなる基油に、フッ素化油およびリチウム系複合石けん増稠剤を含有する潤滑グリース組成物が記載されており、それの評価はピンオンディスク摩耗試験について行われている。 Patent Document 3 describes a lubricating grease composition containing a fluorinated oil and a lithium-based composite soap thickener in a base oil comprising a synthetic hydrocarbon oil, an ester oil or an ether-based synthetic oil, The evaluation is conducted for the pin on disk wear test.
　特許文献４には、極圧性および耐摩耗性にすぐれた潤滑グリース組成物として、パーフルオロポリエーテル基油に増稠剤として脂肪酸金属塩とフッ素樹脂とが混合されたものとして構成されている。 In Patent Document 4, as a lubricating grease composition excellent in extreme pressure property and wear resistance, a composition is prepared by mixing a perfluoropolyether base oil with a fatty acid metal salt and a fluorine resin as a thickener.
特開平７－２６８３７０号公報Japanese Patent Application Laid-Open No. 7-268370 特開２００３－０９６４８０号公報Unexamined-Japanese-Patent No. 2003-096480 特開２００６－１８２９２３号公報JP, 2006-182923, A 特開２００７－１５４０８４号公報JP, 2007-150408, A
　本発明の目的は、非フッ素系基油およびフッ素系基油よりなる基油混合物に増稠剤およびフッ素樹脂を含有させた往復摺動用潤滑グリース組成物であって、往復摺動用潤滑グリースにとって必要な特性を有するものを提供することにある。 An object of the present invention is a lubricating grease composition for reciprocating sliding, in which a thickener and a fluorine resin are contained in a base oil mixture consisting of a non-fluorinated base oil and a fluorinated base oil, which is necessary for lubricating greases for reciprocating sliding. To provide ones having the following characteristics.
　かかる本発明の目的は、非フッ素系基油に脂肪族ジカルボン酸とモノアミドモノカルボン酸または脂肪族モノカルボン酸との複合金属石けん増稠剤を含有させた、滴点が250℃以上の非フッ素系グリースおよび非フッ素系基油と相溶性のないフッ素系基油にフッ素樹脂粉末を含有させたフッ素系グリースの2種のグリース混合物よりなる往復摺動用潤滑グリース組成物によって達成される。 The object of the present invention is non-fluorine having a dropping point of 250 ° C. or more, wherein a non-fluorinated base oil contains a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid or aliphatic monocarboxylic acid. This is achieved by a lubricating grease composition for reciprocating sliding comprising a mixture of two greases of a fluorocarbon resin and a fluorocarbon base oil incompatible with a non-fluorocarbon base oil and a fluorocarbon oil.
　非フッ素系基油に複合金属石けん増稠剤を含有させた非フッ素系グリースおよびフッ素系基油にフッ素樹脂粉末を含有させたフッ素系グリースの2種のグリース混合物よりなり、非フッ素系基油に複合金属石けんを含有させた非フッ素系グリースとして、グリースとして成立する上限温度に相当する滴点が250℃以上であるものを用いることにより、蒸発損失および離油度が少なく、またSRV試験(往復動試験)での摩擦係数の変動幅が小さくかつその変動が少なく、安定している潤滑グリース組成物が得られる。 A non-fluorinated base oil comprising two grease mixtures of a non-fluorinated grease in which a composite metal soap thickener is contained in a non-fluorinated base oil and a fluorine-based grease in which a fluorocarbon powder is contained in a fluorinated base oil. Evaporative loss and oil separation are small by using a non-fluorinated grease containing complex metal soap in it and having a dropping point corresponding to the upper limit temperature established as grease, at 250 ° C. or higher, and the SRV test ( A stable lubricating grease composition is obtained which has a small fluctuation range of the friction coefficient in the reciprocation test and a small fluctuation thereof.
　このように、フッ素系グリースが摺動部に十分保持され難く、また供給され難いような条件下においても、互いに相溶性のない非フッ素系基油およびフッ素系基油よりなる基油混合物中に、金属複合石けん増稠剤およびフッ素樹脂粉末を含有せしめた潤滑グリース組成物を用い、かつ金属複合石けん含有非フッ素系基油(非フッ素系グリース)の滴点が一定温度以上のものを用いることにより、フッ素系グリースの耐熱耐久性を維持しながら、摺動部にグリースを保持し易く、かつ摩擦係数を改善し得るという効果を奏する。 As described above, in a base oil mixture composed of a non-fluorinated base oil and a fluorinated base oil which are incompatible with each other even under conditions where the fluorine-based grease is difficult to be sufficiently held in the sliding portion and difficult to be supplied. Using a lubricating grease composition containing a metal complex soap thickener and a fluorocarbon resin powder, and using a metal complex soap-containing non-fluorine base oil (non-fluorine grease) having a dropping point of a predetermined temperature or more As a result, while maintaining the heat resistance and durability of the fluorine-based grease, it is easy to hold the grease on the sliding portion, and the coefficient of friction can be improved.
　本発明で用いられる基油混合物である非フッ素系基油とフッ素系基油との間では、互いに相溶性のないものが用いられる。互いに相溶性のないということは、これら両者を単純に混合したとき均質な基油混合物を形成し得ないことを意味する。 In the non-fluorinated base oil and the fluorinated base oil which are base oil mixtures used in the present invention, those which are not compatible with each other are used. Incompatibility with one another means that a simple base oil mixture can not be formed when the two are simply mixed.
　非フッ素系基油としては、例えばポリ-α-オレフィン、エチレン-α-オレフィンオリゴマー、ポリブテンまたはこれらの水素化物、アルキルベンゼン、アルキルナフタレン等の合成炭化水素油、ポリアルキレングリコール、ポリフェニルエーテル、アルキル置換ジフェニルエーテル等のエーテル系合成油、トリメリット酸エステル、ピロメリット酸エステル等の芳香族多価カルボン酸エステル、ネオペンチルグリコールエステル、トリメチロールプロパンエステル、ペンタエリスリトールエステル、ジペンタエリスリトールエステル等のポリオールエステル、さらに脂肪族二塩基酸エステル、リン酸エステル、亜リン酸エステル、炭酸エステル等のエステル系合成油、パラフィン系鉱油、ナフテン系鉱油またはこれらを精製した鉱油等の少くとも一種、好ましくは合成炭化水素油またはエーテル系合成油が用いられる。 Non-fluorinated base oils include, for example, poly-α-olefins, ethylene-α-olefin oligomers, polybutenes or their hydrides, synthetic hydrocarbon oils such as alkylbenzenes and alkylnaphthalenes, polyalkylene glycols, polyphenyl ethers, alkyl substituted Synthetic ethers of ethers such as diphenyl ether, aromatic polyvalent carboxylic acid esters such as trimellitic acid ester, pyromellitic acid ester, neopentyl glycol ester, trimethylol propane ester, pentaerythritol ester, polyol ester such as dipentaerythritol ester, Furthermore, ester-based synthetic oils such as aliphatic dibasic acid esters, phosphoric acid esters, phosphites and carbonic esters, paraffinic mineral oils, naphthenic mineral oils, and mineral oils obtained by refining these. Also one, preferably synthetic hydrocarbon oils or ether-based synthetic oil is used.
　これらの非フッ素系基油は、40℃における動粘度(ASTM D445に対応するJIS K2283準拠)が約15～350mm2/秒、好ましくは約20～300mm2/秒のものが一般に用いられる。動粘度がこれ以下のものは高温耐久性が悪く、すなわち蒸発量が多くなり、一方これ以上の動粘度以上のものは、摺動時の隙間への浸透性が悪化し、グリース切れが生じ易くなる。 As these non-fluorinated base oils, those having a kinematic viscosity at 40 ° C. (in accordance with JIS K 2283 corresponding to ASTM D445) of about 15 to 350 mm 2 / sec, preferably about 20 to 300 mm 2 / sec are generally used. If the kinematic viscosity is less than this, the high temperature durability is poor, that is, the evaporation amount is large, while if the kinematic viscosity is more than this, the permeability to the gap at the sliding becomes worse, and grease breakage tends to occur. Become.
　フッ素系基油としては、非フッ素系基油の場合と同じ理由により、40℃における動粘度(JIS K2283準拠)が約15～350mm2/秒、好ましくは約20～300mm2/秒のものが一般に用いられ、より具体的には一般式
　　　RfO(CF2O)x(C2F4O)y(C3F6O)zRf
で表わされるものが用いられる。具体的には、例えば下記一般式(1)～(4)で表わされるようなものが用いられ、この他一般式(5)で表わされるようなものも用いられる。なお、Rfはパーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基等の炭素数1～5、好ましくは1～3のパーフルオロ低級アルキル基である。
(1) RfO(CF2CF2O)m(CF2O)nRf
ここで、m+n=3～200、m:n=10～90:90～10であり、またCF2CF2O基およびCF2O基は主鎖中にランダムに結合しているものであり、テトラフルオロエチレンの光酸化重合で生成した先駆体を完全にフッ素化することによって得られる。
(2) RfO〔CF(CF3)CF2O)〕m(CF2O)nRf
ここで、m+n=3～200、m:n=10～90:90～10であり、またCF(CF3)CF2O基およびCF2O基は主鎖中にランダムに結合しているものであり、ヘキサフルオロプロピレンの光酸化重合で生成した先駆体を完全にフッ素化することによって得られる。
(3) RfO[CF(CF3)CF2O]p(CF2CF2O)q(CF2O)rRf
ここで、p+q+r=3～200でqおよびrは0であり得、(q+r)/p=0～2であり、またCF(CF3)CF2O基、CF2CF2O基およびCF2O基は主鎖中にランダムに結合しているものであり、ヘキサフルオロプロピレンおよびテトラフルオロエチレンの光酸化重合で生成した先駆体を完全にフッ素化することにより得られる。
(4) RfO[CF(CF3)CF2O]s(CF2CF2O)tRf
ここで、s+t=2～200でtは0であり得、t/s=0～2であり、またCF(CF3)CF2O基およびCF2CF2O基は主鎖中にランダムに結合しているものであり、ヘキサフルオロプロピレンおよびテトラフルオロエチレンの光酸化重合で生成した先駆体を完全にフッ素化することにより、あるいはフッ化セシウム触媒の存在下にヘキサフルオロプロピレンオキサイドまたはテトラフルオロエチレンオキサイドをアニオン重合させ、得られた末端-CF(CF3)COF基を有する酸フロライド化合物をフッ素ガスで処理することによって得られる。
(5) F(CF2CF2CF2O)2～100C2F5
これは、フッ化セシウム触媒の存在下に2,2,3,3-テトラフルオロオキセタンをアニオン重合させ、得られた含フッ素ポリエーテル(CH2CF2CF2O)nを紫外線照射下に約160～300℃でフッ素ガスで処理することによって得られる。 The fluorine-based base oil, for the same reason as the case of the non-fluorine-based base oil, kinematic viscosity at 40 ° C. (JIS K2283 compliant) is about 15 ~ 350 mm 2 / sec, it is preferably of about 20 ~ 300 mm 2 / s commonly used, and more specifically the general formula RfO (CF 2 O) x ( C 2 F 4 O) y (C 3 F 6 O) z Rf
The one represented by is used. Specifically, for example, those represented by the following general formulas (1) to (4) are used, and those represented by the other general formula (5) are also used. Rf is a perfluoro lower alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, such as perfluoromethyl group, perfluoroethyl group, perfluoropropyl group and the like.
(1) RfO (CF 2 CF 2 O) m (CF 2 O) n Rf
Here, m + n = 3 to 200, m: n = 10 to 90: 90 to 10, and CF 2 CF 2 O and CF 2 O are randomly bonded in the main chain. It is obtained by completely fluorinating a precursor produced by photooxidation polymerization of tetrafluoroethylene.
(2) RfO [CF (CF 3) CF 2 O ) ] m (CF 2 O) n Rf
Here, m + n = 3 ~ 200 , m: n = 10 ~ 90: 90 to 10, and CF (CF 3) CF 2 O group and CF 2 O group are randomly bonded to the main chain It is obtained by completely fluorinating a precursor produced by photooxidation polymerization of hexafluoropropylene.
(3) RfO [CF (CF 3) CF 2 O] p (CF 2 CF 2 O) q (CF 2 O) r Rf
Here, p + q + r = 3 to 200 and q and r may be 0, (q + r) / p = 0 to 2, and CF (CF 3 ) CF 2 O group, CF 2 CF The 2 O group and the CF 2 O group are randomly bonded in the main chain and can be obtained by completely fluorinating a precursor formed by photooxidation polymerization of hexafluoropropylene and tetrafluoroethylene.
(4) RfO [CF (CF 3) CF 2 O] s (CF 2 CF 2 O) t Rf
Here, t with s + t = 2 ~ 200 can be 0, a t / s = 0 ~ 2, also CF (CF 3) CF 2 O group and CF 2 CF 2 O groups in the main chain By randomly fluorinating a precursor formed by photooxidation polymerization of hexafluoropropylene and tetrafluoroethylene, or by bonding in the presence of a cesium fluoride catalyst, it is randomly bonded. It is obtained by anionically polymerizing fluoroethylene oxide and treating the obtained acid fluoride compound having a terminal —CF (CF 3 ) COF group with fluorine gas.
(5) F (CF 2 CF 2 CF 2 O) 2 to 100 C 2 F 5
This is the anionic polymerization of 2,2,3,3-tetrafluorooxetane in the presence of a cesium fluoride catalyst, and the resulting fluorinated polyether (CH 2 CF 2 CF 2 O) n being irradiated with ultraviolet light for about It is obtained by treatment with fluorine gas at 160 to 300 ° C.
　これらの非フッ素系基油とフッ素系基油とは、一般に前者が1～95重量％、好ましくは6～89重量％に対し、後者が99～5重量％、好ましくは94～11重量％の割合で用いられる。非フッ素系基油の混合割合がこれよりも少ないと、耐荷重性は良くなるものの、耐摩耗性、耐熱性、せん断安定性など劣るようになり、一方これよりも多い混合割合では、耐摩耗性は良くなるもの、耐熱性、耐荷重性、せん断安定性などに劣るようになる。 The non-fluorinated base oil and the fluorinated base oil are generally composed of 1 to 95% by weight, preferably 6 to 89% by weight of the former, and 99 to 5% by weight, preferably 94 to 11% by weight of the latter. Used in proportions. If the mixing ratio of the non-fluorinated base oil is less than this, the load resistance improves, but the wear resistance, heat resistance, shear stability, etc. become inferior, while if the mixing ratio is more than this, the wear resistance It becomes poor in heat resistance, load resistance, shear stability, etc.
　増稠剤としての複合金属石けんは、脂肪族ジカルボン酸とモノアミドモノカルボン酸または脂肪族モノカルボン酸との複合金属石けんとして形成される。複合金属石けんの形成は、後述の如く潤滑グリース組成物の調製時に行われる。 Complex metal soaps as thickeners are formed as complex metal soaps of aliphatic dicarboxylic acids and monoamide monocarboxylic acids or aliphatic monocarboxylic acids. The formation of the complex metal soap is carried out during the preparation of the lubricating grease composition as described below.
　脂肪族ジカルボン酸としては、炭素数2～20の飽和または不飽和のジカルボン酸が用いられる。飽和ジカルボン酸としては、例えばシュウ酸、マロン酸、コハク酸、メチルコハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ノナメチレンジカルボン酸、デカメチレンジカルボン酸、ウンデカンジカルボン酸、ドデカンジカルボン酸、トリデカンジカルボン酸、テトラデカンジカルボン酸、ペンタデカンジカルボン酸、ヘキサデカンジカルボン酸、ヘプタデカンジカルボン酸、オクタデカンジカルボン酸等が挙げられ、好ましくはアジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ノナメチレンジカルボン酸、デカメチレンジカルボン酸、ウンデカンジカルボン酸、ドデカンジカルボン酸、トリデカンジカルボン酸、テトラデカンジカルボン酸、ペンタデカンジカルボン酸、ヘキサデカンジカルボン酸、ヘプタデカンジカルボン酸、オクタデカンジカルボン酸等が用いられる。また、不飽和ジカルボン酸としては、例えばマレイン酸、フマル酸、さらに2-メチレンコハク酸、2-エチレンコハク酸、2-メチレングルタル酸等のアルケニルコハク酸などが用いられる。これらの飽和または不飽和のジカルボン酸は、単独であるいは2種以上混合して用いられる。 As aliphatic dicarboxylic acid, saturated or unsaturated dicarboxylic acid having 2 to 20 carbon atoms is used. Examples of saturated dicarboxylic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid, undecanedicarboxylic acid And dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid and the like, and preferably adipic acid, pimelic acid, suberic acid, azelaic acid, sebacine Acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexene Decanedicarboxylic acid, hepta-decane dicarboxylic acid, octadecane dicarboxylic acid, or the like is used. Further, as unsaturated dicarboxylic acid, for example, maleic acid, fumaric acid, and further alkenyl succinic acid such as 2-methylene succinic acid, 2-ethylene succinic acid, 2-methylene glutaric acid and the like are used. These saturated or unsaturated dicarboxylic acids may be used alone or in combination of two or more.
　モノアミドモノカルボン酸は、上記ジカルボン酸のモノカルボキシル基がアミド化されたものであり、アミド化されるアミンとしては、例えばブチルアミン、アミルアミン、へキシルアミン、へプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ラウリルアミン、ミリスチルアミン、パルミチルアミン、ステアリルアミン、ベヘニルアミン等の脂肪族第1級アミン、ジプロピルアミン、ジイソプロピルアミン、ジブチルアミン、ジアミルアミン、ジラウリルアミン、モノメチルラウリルアミン、ジステアリルアミン、モノメチルステアリルアミン、ジミリスチルアミン、ジパルミチルアミン等の脂肪族第2級アミン、アリルアミン、ジアリルアミン、オレイルアミン、ジオレイルアミン等の脂肪族不飽和アミン、シクロプロピルアミン、シクロブチルアミン、シクロペンチルアミン、シクロヘキシルアミン等の脂環式アミン、アニリン、メチルアニリン、エチルアニリン、ベンジルアミン、ジベンジルアミン、ジフェニルアミン、α-ナフチルアミン等の芳香族アミンなどが挙げられ、好ましくはへキシルアミン、へプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ラウリルアミン、ミリスチルアミン、パルミチルアミン、ステアリルアミン、ベヘニルアミン、ジブチルアミン、ジアミルアミン、モノメチルラウリルアミン、モノメチルステアリルアミン、オレイルアミン等が用いられる。 The monoamide monocarboxylic acid is obtained by amidating the monocarboxylic group of the above dicarboxylic acid, and as the amine to be amidated, for example, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine Aliphatic primary amines such as myristylamine, palmitylamine, stearylamine, behenylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dilaurylamine, monomethyllaurylamine, distearylamine, monomethylstearylamine, Aliphatic secondary amines such as dimyristylamine and dipalmitylamine, aliphatic unsaturated amines such as allylamine, diallylamine, oleylamine and dioleylamine, cyclopropyl And cycloaliphatic amines such as cyclobutylamine, cyclopentylamine and cyclohexylamine; aromatic amines such as aniline, methyl aniline, ethyl aniline, benzyl aniline, benzylamine, dibenzylamine, diphenylamine and α-naphthylamine; Xylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, palmitylamine, stearylamine, behenylamine, dibutylamine, diamylamine, monomethyl laurylamine, monomethyl stearylamine, oleylamine and the like are used.
　また、脂肪族モノカルボン酸としては、例えば酪酸、カプロン酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、12-ヒドロキシステアリン酸、ベヘニン酸等の飽和脂肪酸またはオレイン酸、リノール酸、リノレン酸、リシノレン酸等の不飽和脂肪酸が用いられ、好ましくは12-ヒドロキシステアリン酸が用いられる。 Moreover, as aliphatic monocarboxylic acids, for example, saturated fatty acids such as butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid or the like Unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and ricinolenic acid are used, preferably 12-hydroxystearic acid.
　これらの脂肪族ジカルボン酸とモノアミドモノカルボン酸または脂肪族モノカルボン酸とは、前者に対し後者が0.1～10、好ましくは0.5～5のモル比で用いられる。これ以外の混合割合で用いられると、滴点が低下するなどして好ましくない。これら両者は、水酸化物、酸化物等の形で用いられるリチウム、ナトリウム、カリウム、カルシウム、バリウム、マグネシウム、銅、鉄、コバルト、亜鉛、アルミニウム等の金属化合物によって複合金属石けんを形成させて用いられるが、好ましくは複合バリウム石けんまたは複合リチウム石けんとして用いられる。複合金属石けん調製に用いられる金属化合物は、けん化反応に必要な理論量に対しほぼ当量程度用いられる。 These aliphatic dicarboxylic acids and monoamide monocarboxylic acids or aliphatic monocarboxylic acids are used at a molar ratio of 0.1 to 10, preferably 0.5 to 5, with respect to the former. When it is used at a mixing ratio other than this, the dropping point is lowered, which is not preferable. Both of them are used in the form of complex metal soap with metal compounds such as lithium, sodium, potassium, calcium, barium, magnesium, copper, iron, cobalt, zinc and aluminum used in the form of hydroxides and oxides. Preferably, it is used as a complex barium soap or a complex lithium soap. The metal compound used to prepare the complex metal soap is used in an amount approximately equivalent to the theoretical amount required for the saponification reaction.
　また、フッ素樹脂粉末としては、PTFE粉末、HFP粉末、パーフルオロアルキレン樹脂粉末等が用いられる。これらのフッ素樹脂粉末は、一般にその平均一次粒径が約500μm以下、好ましくは約0.1～30μmのものが用いられる。 Further, as the fluorocarbon resin powder, PTFE powder, HFP powder, perfluoroalkylene resin powder or the like is used. Generally, fluorine resin powders having an average primary particle size of about 500 μm or less, preferably about 0.1 to 30 μm, are used.
　PTFE(ポリテトラフルオロエチレン)は、テトラフルオロエチレンの乳化重合、けん濁重合、溶液重合などの方法によってポリテトラフルオロエチレンを製造し、それを熱分解、電子線照射分解、物理的粉砕などの方法によって処理して数平均分子量Mnを約1000～1000000程度としたものが用いられる。また、HFP粉末の場合には、テトラフルオロエチレンとヘキサフルオロプロペンとの共重合反応および低分子量化処理も、ポリテトラフルオロエチレンの場合と同様にして行われ、数平均分子量Mnを約1000～600000程度としたものが用いられる。なお、分子量の制御は、共重合反応時に連鎖移動剤を用いても行うことができる。 PTFE (polytetrafluoroethylene) manufactures polytetrafluoroethylene by methods such as emulsion polymerization, suspension polymerization, solution polymerization and the like of tetrafluoroethylene, and methods such as thermal decomposition, electron beam irradiation decomposition, physical pulverization and the like And those having a number average molecular weight Mn of about 1000 to 1,000,000 are used. Further, in the case of HFP powder, the copolymerization reaction of tetrafluoroethylene and hexafluoropropene and the molecular weight reduction treatment are also carried out in the same manner as in the case of polytetrafluoroethylene, and the number average molecular weight Mn is about 1000 to 600000. The degree is used. The control of the molecular weight can also be carried out by using a chain transfer agent at the time of the copolymerization reaction.
　複合金属石けん増稠剤含有非フッ素系基油であるグリース(非フッ素系グリース)およびフッ素樹脂粉末含有フッ素系基油であるグリース(フッ素系グリース)の2種類のグリースを混合することによって、本発明の潤滑グリース組成物は調製される。 By mixing two types of grease: grease (non-fluorinated grease), which is a non-fluorinated base oil containing a complex metal soap thickener, and grease (fluorinated grease), which is a fluorinated base oil containing fluorine resin powder. The lubricating grease composition of the invention is prepared.
　複合金属石けんの形成および潤滑グリース組成物の調製は、次の如くにして行われる。
　(a-1) 加熱攪拌が可能な反応釜に、非フッ素系基油、脂肪族ジカルボン酸およびモノアミドモノカルボン酸または脂肪族モノカルボン酸を加え、攪拌可能な温度であり、反応を効率的に進めかつ基油の劣化を生じさせない温度である約80～180℃に加熱して攪拌し、そこに金属水酸化物または金属酸化物を加えて複合金属石けんを非フッ素系基油中で形成させる。冷却後、そこにアミン系酸化防止剤等を所定量、例えば非フッ素系基油中約0.1～5重量％を占めるような割合で配合し、3本ロールミルまたは高圧ホモジナイザで混練して、非フッ素系グリースを調製する。混練に先立って、最初に用いられた非フッ素系基油以外の他の非フッ素系基油を添加して用いることもできる。
　(a-2) フッ素系基油とフッ素樹脂粉末とを混合釜中で混ぜ、その後3本ロールミルまたは高圧ホモジナイザを用いて混練し、フッ素系グリースを調製する。
　(a-3) これら2種類のグリースを混合釜中で混ぜ、3本ロールミルまたは高圧ホモジナイザ、好ましくは3本ロールミルを用いて混練し、潤滑グリース組成物を調製する。なお、混練に用いられる3本ロールミルとしては、一般に油圧式のものが用いられる。 The formation of the complex metal soap and the preparation of the lubricating grease composition are carried out as follows.
(a-1) A non-fluorinated base oil, an aliphatic dicarboxylic acid and a monoamide monocarboxylic acid or an aliphatic monocarboxylic acid are added to a reaction vessel capable of heating and stirring, and the temperature is such that stirring is possible, and the reaction is efficiently performed. Advanced and heated to about 80-180 ° C., which is a temperature that does not cause deterioration of the base oil, and stirred, to which a metal hydroxide or metal oxide is added to form a composite metal soap in a non-fluorinated base oil . After cooling, a predetermined amount of amine antioxidant, etc. is blended therein, for example, in a proportion to occupy about 0.1 to 5% by weight in a non-fluorinated base oil, and it is kneaded using a triple roll mill or a high pressure homogenizer to obtain non-fluorine. Prepare a grease system. It is also possible to add and use other non-fluorinated base oils other than the first used non-fluorinated base oil prior to kneading.
(a-2) The fluorinated base oil and the fluorocarbon resin powder are mixed in a mixing pot, and thereafter, they are kneaded using a three-roll mill or a high pressure homogenizer to prepare a fluorinated grease.
(a-3) These two types of greases are mixed in a mixing kettle and kneaded using a three-roll mill or a high-pressure homogenizer, preferably a three-roll mill, to prepare a lubricating grease composition. In addition, as a three-roll mill used for kneading, a hydraulic type is generally used.
　(b) 上記の如くにして調製された非フッ素系グリースに、フッ素系基油およびフッ素樹脂を加え、混合釜中で混ぜた後、3本ロールミルまたは高圧ホモジナイザで混練しても、本発明の潤滑グリース組成物を調製することもできる。 (b) A fluorine-based base oil and a fluorine resin are added to the non-fluorinated grease prepared as described above, and they are mixed in a mixing kettle and then kneaded using a triple roll mill or a high pressure homogenizer. Lubricating grease compositions can also be prepared.
　この際、複合金属石けん増稠剤含有非フッ素系基油であるグリース(非フッ素系グリース)は、グリースとして成立する上限温度に相当する滴点が250℃以上のものが用いられる。滴点が250℃未満の非フッ素系グリースを用いると、120～150℃あるいはそれ以上の温度での往復摺動用途への適用に際し、製品信頼性の低下が問題となる場合がある。なお、滴点は、ISO 2176に対応するJIS K2220.8に準拠して測定される。 At this time, as the grease (non-fluorinated grease) which is a non-fluorinated base oil containing a complex metal soap thickener, one having a dropping point of 250 ° C. or higher corresponding to the upper limit temperature established as a grease is used. When using a non-fluorinated grease having a dropping point of less than 250 ° C., there may be a problem of reduced product reliability when applied to reciprocating sliding applications at temperatures of 120 to 150 ° C. or more. The dropping point is measured in accordance with JIS K 2220.8 corresponding to ISO 2176.
　以上の必須各成分よりなる潤滑グリース組成物において、非フッ素系基油は1～90重量％、好ましくは5～80重量％の割合で、非フッ素系基油と前記の如き混合割合で用いられるフッ素系基油は5～80重量％、好ましくは10～80重量％の割合で、複合金属石けんは0.5～30重量％、好ましくは1～25重量％の割合で、またフッ素樹脂粉末は0.1～20重量％、好ましくは1～15重量％の割合でそれぞれ用いられる。 In the lubricating grease composition comprising the above essential components, the non-fluorinated base oil is used in a proportion of 1 to 90% by weight, preferably 5 to 80% by weight, with the non-fluorinated base oil in the mixing ratio as described above The content of the fluorinated base oil is 5 to 80% by weight, preferably 10 to 80% by weight, the complex metal soap is 0.5 to 30% by weight, preferably 1 to 25% by weight, and the fluorocarbon resin powder is 0.1 to It is used in a proportion of 20% by weight, preferably 1 to 15% by weight.
　このような割合での各成分の配合により、非フッ素系基油にあっては、フッ素系基油に相溶性のないあるいは乏しい増稠剤の添加を可能とし、それによって耐摩耗性の向上、摩擦係数の低減、防錆性や腐食防止効果の向上を図ることができ、フッ素系基油にあっては、耐熱性の向上を図ることができ、複合金属石けんにあっては、耐摩耗性の向上が図られ、またフッ素樹脂粉末にあっては、フッ素系基油と複合金属石けんとの相溶性の向上を図ることができる。 By blending the components in such proportions, in the case of a non-fluorinated base oil, it becomes possible to add a thickening agent which is incompatible or poor in the fluorinated base oil, thereby improving the wear resistance, The coefficient of friction can be reduced, the antirust property and the corrosion prevention effect can be improved, and in the case of a fluorine-based base oil, the heat resistance can be improved, and in the case of a complex metal soap, the wear resistance In the case of the fluorocarbon resin powder, the compatibility between the fluorocarbon base oil and the complex metal soap can be improved.
　潤滑グリース組成物中にはさらに、酸化防止剤、防錆剤、腐食防止剤、極圧剤、油性剤、固体潤滑剤などの従来潤滑剤に使用されている添加剤を必要に応じて配合することができる。酸化防止剤としては、例えば2,6-ジ第3ブチル-4-メチルフェノール、4,4′-メチレンビス(2,6-ジ第3ブチルフェノール)等のフェノール系の酸化防止剤、C4～C20のアルキル基を有するアルキルジフェニルアミン、トリフェニルアミン、フェニル-α-ナフチルアミン、アルキル化フェニル-α-ナフチルアミン、フェノチアジン、アルキル化フェノチアジン等のアミン系の酸化防止剤、さらにはリン系酸化防止剤、イオウ系酸化防止剤などが挙げられる。 In the lubricating grease composition, additives used in conventional lubricants, such as antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure agents, oil agents, solid lubricants, etc. are further incorporated as necessary. be able to. As the antioxidant, for example, phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis (2,6-di-tert-butylphenol), C 4 -C Amine-based antioxidants such as alkyldiphenylamines having 20 alkyl groups, triphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, phenothiazines, alkylated phenothiazines, and further phosphorus-based antioxidants, sulfur And antioxidants and the like.
　防錆剤としては、例えば脂肪酸、脂肪酸金属塩、脂肪酸アミン、アルキルスルホン酸金属塩、アルキルスルホン酸アミン塩、酸化パラフィン、ポリオキシエチレンアルキルエーテル等が挙げられ、また腐食防止剤としては、例えばベンゾトリアゾール、ベンゾイミダゾール、チアジアゾール等が挙げられる。 Examples of the antirust agent include fatty acids, fatty acid metal salts, fatty acid amines, alkylsulfonic acid metal salts, alkylsulfonic acid amine salts, oxidized paraffins, oxidized paraffins, polyoxyethylene alkyl ethers and the like, and corrosion inhibitors include, for example, benzo Triazole, benzimidazole, thiadiazole and the like can be mentioned.
　極圧剤としては、例えばリン酸エステル、亜リン酸エステル、リン酸エステルアミン塩等のリン系化合物、スルフィド類、ジスルフィド類等のイオウ系化合物、ジアルキルジチオリン酸金属塩、ジアルキルジチオカルバミン酸金属塩等のイオウ系化合物金属塩、塩素化パラフィン、塩素化ジフェニル等の塩素系化合物などが挙げられる。 As an extreme pressure agent, for example, phosphorus compounds such as phosphoric acid ester, phosphorous acid ester, phosphoric acid ester amine salt, sulfur compounds such as sulfides and disulfides, metal salts of dialkyl dithiophosphates, metal salts of dialkyl dithiocarbamates, etc. Sulfur-based compound metal salts, chlorinated paraffins, chlorinated compounds such as chlorinated diphenyl, and the like.
　油性剤としては、例えば脂肪酸またはそのエステル、高級アルコール、多価アルコールまたはそのエステル、脂肪族エステル、脂肪族アミン、脂肪酸モノグリセライド、モンタンワックス、アミド系ワックス等が挙げられる。また、他の固体潤滑剤としては、例えば二硫化モリブデン、グラファイト、窒化ホウ素、窒化シラン、メラミンシアヌレート等が挙げられる。これらの他の固体潤滑剤についても、その平均一次粒径は30μm以下、好ましくは0.1～20μmのものが用いられる。 Examples of the oil agent include fatty acids or esters thereof, higher alcohols, polyhydric alcohols or esters thereof, aliphatic esters, aliphatic amines, fatty acid monoglycerides, montan waxes, amide waxes and the like. Moreover, as another solid lubricant, for example, molybdenum disulfide, graphite, boron nitride, silane nitride, melamine cyanurate and the like can be mentioned. Also for these other solid lubricants, those having an average primary particle size of 30 μm or less, preferably 0.1 to 20 μm, are used.
　さらに、増稠剤として従来一般的に使用されている他の増稠剤、例えばシリカ、粘土、グラファイト、酸化亜鉛、ウレア化合物、ポリエチレン、ポリプロピレン、ポリアミド、有機顔料、金属石けん等を適宜添加して用いることもできる。 In addition, other thickeners generally and conventionally used as thickeners, such as silica, clay, graphite, zinc oxide, urea compounds, polyethylene, polypropylene, polyamide, organic pigments, metal soaps and the like are appropriately added. It can also be used.
　次に、実施例について本発明を説明する。 The invention will now be described by way of example.
　参考例１
　ポリ-α-オレフィン油(40℃粘度：30mm2/秒)中で、増稠剤として非フッ素系グリース中30重量％を占めるセバシン酸とセバシン酸モノステアリルアミドとのバリウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(KING INDUSTRIES製品NA-LUBE AO-120；アルキルジフェニルアミン)を添加した後、3本ロールミルで2回混練して、グリースAを調製した。得られたグリースAの滴点は、283℃であった。 Reference Example 1
Barium complex soap of sebacic acid and sebacic acid monostearylamide, which accounts for 30% by weight in non-fluorinated grease as thickener, in poly-α-olefin oil (40 ° C. viscosity: 30 mm 2 / s) Compound (2) was synthesized by method (a-1), to which 2% by weight of amine antioxidant (KING INDUSTRIES product NA-LUBE AO-120; alkyl diphenylamine) was added, and the mixture was kneaded twice with a three-roll mill, Grease A was prepared. The dropping point of the obtained grease A was 283 ° C.
　参考例２
　ポリ-α-オレフィン油(40℃粘度：30mm2/秒および400mm2/秒のものを1：1の重量比で混合したもの)中で、増稠剤として非フッ素系グリース中25重量％を占めるアゼライン酸とアゼライン酸モノオクチルアミドとのバリウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースBを調製した。得られたグリースBの滴点は、277℃であった。 Reference Example 2
25% by weight in non-fluorinated grease as thickener, in poly-α-olefin oil (40 ° C. viscosity: 30 mm 2 / s and 400 mm 2 / s mixed in a weight ratio of 1: 1) as thickener A barium complex soap consisting of azelaic acid and monooctylamide of azelaic acid was synthesized by the method (a-1) as described above, to which 2% by weight of amine antioxidant (NA-LUBE AO-120) was added. Thereafter, the mixture was kneaded twice with a three-roll mill to prepare grease B. The dropping point of the obtained grease B was 277 ° C.
　参考例３
　アルキルナフタレン(40℃粘度：114mm2/秒)中で、増稠剤として非フッ素系グリース中25重量％を占めるアゼライン酸とアゼライン酸モノオクチルアミドとのバリウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースCを調製した。得られたグリースCの滴点は、273℃であった。 Reference Example 3
A method as described above (a-) of a barium complex soap of azelaic acid and azelaic acid monooctylamide, which comprises 25% by weight of a nonfluorinated grease as a thickener, in alkyl naphthalene (40 ° C. viscosity: 114 mm 2 / s) After synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, the mixture was kneaded twice with a three-roll mill to prepare grease C. The dropping point of the obtained grease C was 273 ° C.
　参考例４
　ジフェニルエーテル油(40℃粘度：100mm2/秒)中で、増稠剤として非フッ素系グリース中15重量％を占めるセバシン酸とセバシン酸モノステアリルアミドとのバリウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースDを調製した。得られたグリースDの滴点は、262℃であった。 Reference Example 4
A method as described above (a-) of a barium complex soap of sebacic acid and sebacic acid monostearylamide which accounts for 15% by weight in non-fluorinated grease as a thickener in diphenyl ether oil (40 ° C. viscosity: 100 mm 2 / s) After synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, the mixture was kneaded twice with a three-roll mill to prepare grease D. The dropping point of the obtained grease D was 262 ° C.
　参考例５
　ジフェニルエーテル油(40℃粘度：100mm2/秒)中で、増稠剤として非フッ素系グリース中25重量％を占めるセバシン酸とセバシン酸モノステアリルアミドとのバリウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースEを調製した。得られたグリースEの滴点は、270℃であった。 Reference Example 5
A method as described above (a-) of a barium complex soap of sebacic acid and sebacic acid monostearylamide which accounts for 25% by weight in non-fluorinated grease as a thickener in diphenyl ether oil (40 ° C. viscosity: 100 mm 2 / s) After synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, the mixture was kneaded twice with a three-roll mill to prepare grease E. The dropping point of the obtained grease E was 270 ° C.
　参考例６
　ポリ-α-オレフィン油(40℃粘度：46mm2/秒)中で、増稠剤中として非フッ素系グリース中20重量％を占めるアゼライン酸と12-ヒドロキシステアリン酸とのリチウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースFを調製した。得られたグリースFの滴点は、280℃であった。 Reference Example 6
Lithium complex soap of azelaic acid and 12-hydroxystearic acid in poly-α-olefin oil (40 ° C. viscosity: 46 mm 2 / s), accounting for 20% by weight in non-fluorinated grease as thickener in the above-mentioned (A-1), 2 wt% of an amine antioxidant (NA-LUBE AO-120) was added thereto, and the mixture was kneaded twice with a three-roll mill to prepare grease F. . The dropping point of the obtained grease F was 280 ° C.
　参考例７
　ジフェニルエーテル油(40℃粘度：100mm2/秒)中で、増稠剤として非フッ素系グリース中20重量％を占めるセバシン酸と12-ヒドロキシステアリン酸とのリチウム複合石けんを前記の如き方法(a-1)で合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースGを調製した。得られたグリースGの滴点は、269℃であった。 Reference Example 7
A method as described above (a-) a lithium complex soap of sebacic acid and 12-hydroxystearic acid which accounts for 20% by weight in non-fluorinated grease as a thickener in diphenyl ether oil (40 ° C. viscosity: 100 mm 2 / s) A grease G was prepared by synthesizing it in 1) and adding 2% by weight of an amine antioxidant (NA-LUBE AO-120) thereto, followed by kneading twice with a three-roll mill. The dropping point of the obtained grease G was 269 ° C.
　参考例８
　ポリ-α-オレフィン油(40℃粘度：30mm2/秒)中で、増稠剤中として非フッ素系グリース中10重量％を占める12-ヒドロキシステアリン酸のリチウム石けんを合成し、これに2重量％のアミン系酸化防止剤(NA-LUBE AO-120)を添加した後、3本ロールミルで2回混練して、グリースHを調製した。得られたグリースHの滴点は、182℃であった。 Reference Example 8
Synthesized lithium soap of 12-hydroxystearic acid in poly-α-olefin oil (40 ° C viscosity: 30 mm 2 / s) and accounting for 10% by weight in non-fluorinated grease as thickener, 2 weight on this % Grease was added thereto, and then the mixture was kneaded twice with a three-roll mill to prepare grease H. The dropping point of the obtained grease H was 182 ° C.
　参考例９
　分子構造RfO〔CF(CF3)CF2O〕mRfを有する基油(40℃粘度：230mm2/秒)に、フッ素系グリース中18重量％を占める量のPTFE粉末(平均粒子径0.3μm)を混合し、3本ロールミルで2回混練して、グリースIを調製した。得られたグリースIの滴点は、300℃以上であった。 Reference Example 9
Molecular powder RfO [CF (CF 3 ) CF 2 O] PTFE powder (average particle size 0.3 μm) in an amount of 18% by weight in fluorine-based grease with base oil (40 ° C viscosity: 230 mm 2 / s) having m Rf The mixture was mixed and kneaded twice with a three-roll mill to prepare grease I. The dropping point of the obtained grease I was 300 ° C. or more.
　参考例１０
　分子構造RfO(CF2CF2O)m(CF2O)nRfを有する基油(40℃粘度：85mm2/秒)に、フッ素系グリース中27重量％を占める量のPTFE粉末(平均粒子径0.3μm)を混合し、3本ロールミルで2回混練して、グリースIIを調製した。得られたグリースIIの滴点は、300℃以上であった。 Reference Example 10
PTFE powder (average particles) in an amount of 27% by weight in a fluorine-based grease in a base oil (40 ° C. viscosity: 85 mm 2 / s) having a molecular structure RfO (CF 2 CF 2 O) m (CF 2 O) n Rf Grease II was prepared by mixing 0.3 μm in diameter and kneading twice with a three-roll mill. The dropping point of the obtained grease II was 300 ° C. or more.
　参考例１１
　分子構造RfO(CF2CF2O)m(CF2O)nRfを有する基油(40℃粘度：85mm2/秒)に、フッ素系グリース中15重量％を占める量のPTFE粉末(平均粒子径0.3μm)を混合し、3本ロールミルで2回混練して、グリースIIIを調製した。得られたグリースIIIの滴点は、300℃以上であった。 Reference Example 11
PTFE powder (average particles) in an amount of 15% by weight in a fluorine-based grease in a base oil (40 ° C. viscosity: 85 mm 2 / s) having a molecular structure RfO (CF 2 CF 2 O) m (CF 2 O) n Rf Grease III was prepared by mixing 0.3 μm in diameter and kneading twice with a three-roll mill. The dropping point of the obtained grease III was 300 ° C. or more.
　参考例１２
　分子構造F(CF2CF2CF2O)2～100C2F5を有する基油(40℃粘度：65mm2/秒)に、フッ素系グリース中31重量％を占める量のPTFE粉末(平均粒子径0.3μm)を混合し、3本ロールミルで2回混練して、グリースIVを調製した。得られたグリースIVの滴点は、300℃以上であった。 Reference Example 12
PTFE powder (average amount of 31% by weight of fluorine-based grease in base oil having a molecular structure F (CF 2 CF 2 CF 2 O) 2 to 100 C 2 F 5 (40 ° C. viscosity: 65 mm 2 / sec) The particle size was 0.3 μm, and the mixture was kneaded twice with a three-roll mill to prepare Grease IV. The dropping point of the obtained grease IV was 300 ° C. or more.
　実施例１～８、比較例１～５
　上記各参考例で調製された非フッ素系グリースA～Hおよびフッ素系グリースI～IVの内の1種または2種を所定の重量比で混合し、混合釜中で十分に攪拌混合した後、3本ロールで2回混練し、潤滑グリース組成物を調製した。 Examples 1 to 8 and Comparative Examples 1 to 5
After one or two of the non-fluorinated greases A to H and the fluorinated greases I to IV prepared in each of the above reference examples are mixed in a predetermined weight ratio and thoroughly mixed in a mixing kettle, It knead | mixed twice with 3 rolls, and prepared the lubricating grease composition.
　調製された潤滑グリース組成物について、次の各項目の測定を行った。
　　蒸発損失(耐熱性)：直径37mm、高さ5mmのアルミニウム製皿に、各試料
　　　　　　　　　　　の比重に応じ、例えば比重1の場合0.3gに相当する
　　　　　　　　　　　重量の試料を均一に塗布し、150℃の恒温槽中に24
　　　　　　　　　　　時間静置した後恒温槽から取り出し、試料の蒸発損
　　　　　　　　　　　失を算出
　　　　　　　　　　　(この値が小さい程良い)
　　離油度(耐熱性)：JIS K2220.11準拠
　　　　　　　　　　180℃、24時間後の離油度を測定
　　　　　　　　　　(この値が小さい程良い)
　　SRV試験(往復動試験)：ASTM D5707準拠
　　　　　　　　　　　　 試験片100CR6シリンダ／100CR6プレート
　　　　　　　　　　　　 試験条件　　温度：室温
　　　　　　　　　　　　 　　　　　　荷重：50N
　　　　　　　　　　　　 　　　　　　摺動幅：4mm
　　　　　　　　　　　　 　　　　　　振動数：10Hz
　　　　　　　　　　　　 　　　　　　試験時間：1時間
　　　　　　　　　　　　 上記試験条件下で、試験後の摩擦係数、試験中
　　　　　　　　　　　　 の摩擦係数の挙動を評価
　　　　　　　　　　　　 摩擦係数の挙動については、試験開始10～60分
　　　　　　　　　　　　 間の間で摩擦係数の(最大値)－(最小値)＝変動
　　　　　　　　　　　　 幅とし、摩擦係数の変動が少なく、安定してい
　　　　　　　　　　　　 る場合を○、摩擦係数の変動が大きく、安定し
　　　　　　　　　　　　 ない場合を×と評価した The following items were measured for the prepared lubricating grease composition.
Evaporative loss (heat resistance): A sample of weight equivalent to 0.3 g in the case of specific gravity 1 is uniformly coated on an aluminum plate with a diameter of 37 mm and a height of 5 mm according to the specific gravity of each sample, for example. During 24
After standing for a while, take out from the thermostat and calculate the evaporation loss of the sample (the smaller this value, the better)
Oil separation degree (heat resistance): Measure the oil separation degree after 24 hours at 180 ° C according to JIS K 2220.11 (The smaller the value, the better)
SRV test (reciprocation test): According to ASTM D5707 Test piece 100 CR 6 cylinder / 100 CR 6 plate Test conditions Temperature: room temperature Load: 50 N
Sliding width: 4 mm
Frequency: 10 Hz
Test time: 1 hour Under the above test conditions, evaluate the behavior of the coefficient of friction after the test and the coefficient of friction during the test For the behavior of the coefficient of friction, the maximum value of the coefficient of friction between 10 and 60 minutes from the start of the test -(Minimum value) = fluctuation width, the fluctuation of the friction coefficient was small and stable was evaluated as ○, and the friction coefficient fluctuation was large and unstable, it was evaluated as ×
　測定結果は、次の表１(実施例)および表２(比較例)に示される。
Figure JPOXMLDOC01-appb-I000001
　　　　　　　　　　　　表２　　　　　　　　　　　　
　　　比較例　　　　   １ 　 ２ 　 ３ 　 ４ 　 ５ 
〔非フッ素系グリース〕                                            
 　A　　　　  (重量%)  100　 － 　 － 　 － 　 － 
 　B　　　　  (重量%)  － 　 － 　 － 　 － 　 － 
 　C　　　　  (重量%)  － 　 － 　 － 　 － 　 － 
 　D　　　　  (重量%)  － 　 － 　 － 　 － 　 － 
 　E　　　　  (重量%)  － 　  3 　 － 　 － 　 － 
 　F　　　　  (重量%)  － 　 － 　 － 　 － 　 － 
 　G　　　　  (重量%)  － 　 － 　 － 　 － 　 － 
 　H　　　　  (重量%)  － 　 － 　 80 　 － 　 － 
〔フッ素系グリース〕                                   
 　I　　　　  (重量%)  － 　 － 　 20 　 100　 － 
 　II 　　　  (重量%)  － 　 － 　 － 　 － 　 100
 　III 　　　 (重量%)  － 　 97 　 － 　 － 　 － 
 　IV 　　　  (重量%)  － 　 － 　 － 　 － 　 － 
〔測定項目〕                          
 蒸発損失　　 (重量%) 14.0　 0.6　13.9　 1.8　 0.4
 離油度　　　 (重量%)  2.4　 4.5　 5.2　 5.5　 5.0
 SRV試験
　1時間後摩擦係数　　 0.170 0.240 0.130 0.279 0.232
　変動幅　　   　　　 0.015 0.155 0.025 0.076 0.204
　摩擦係数挙動　　     ○ 　 × 　 ○ 　 × 　 ×  The measurement results are shown in the following Table 1 (Example) and Table 2 (Comparative Example).
Figure JPOXMLDOC01-appb-I000001
Table 2
Comparative Example 1 2 3 4 5
[Non-fluorinated grease]
A (% by weight) 100----
B (% by weight)-----
C (% by weight)-----
D (% by weight)-----
E (% by weight)-3---
F (% by weight)-----
G (% by weight)-----
H (% by weight)--80--
[Fluorine-based grease]
I (% by weight)--20 100-
II (% by weight)----100
III (% by weight)-97---
IV (% by weight)-----
〔Measurement item〕
Evaporative loss (% by weight) 14.0 0.6 13.9 1.8 0.4
Oil removal degree (% by weight) 2.4 4.5 5.2 5.5 5.0
SRV test 1 hour friction coefficient 0.170 0.240 0.130 0.279 0.232
Fluctuation range 0.015 0.155 0.025 0.076 0.204
Coefficient of friction behavior ○ × ○ × ×
　本発明に係る潤滑グリース組成物は、往復摺動用潤滑グリースとして、例えば120～150℃もしくはそれ以上の高温条件下で使用されるマイクロスイッチや電磁駆動弁等のアクチュエータ部位などに用いられる。この他に、往復摺動用潤滑グリースとして作用するガイドレール、スライドレール、ピストン、カム機構等の部位に好適に用いられる。 The lubricating grease composition according to the present invention is used as a lubricating grease for reciprocating sliding, for example, for actuator parts such as micro switches and electromagnetically driven valves used under high temperature conditions of 120 to 150 ° C. or more. In addition to this, it is suitably used for parts such as a guide rail, a slide rail, a piston, a cam mechanism, etc. that act as lubricating grease for reciprocating sliding.

Claims (15)

  1. 　非フッ素系基油に脂肪族ジカルボン酸とモノアミドモノカルボン酸または脂肪族モノカルボン酸との複合金属石けん増稠剤を含有させた、滴点が250℃以上の非フッ素系グリースおよび非フッ素系基油と相溶性のないフッ素系基油にフッ素樹脂粉末を含有させたフッ素系グリースの2種のグリース混合物よりなる往復摺動用潤滑グリース組成物。 A non-fluorinated grease and a non-fluorinated group having a dropping point of 250 ° C. or more, wherein a non-fluorinated base oil contains a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid or aliphatic monocarboxylic acid, A lubricating grease composition for reciprocating sliding comprising a mixture of two greases of a fluorine-based grease in which a fluorine-based base oil incompatible with oil contains a fluorine resin powder.
  2. 　非フッ素系基油が合成炭化水素油またはエーテル系合成油である請求項１記載の往復摺動用潤滑グリース組成物。 The lubricating grease composition for reciprocating sliding according to claim 1, wherein the non-fluorinated base oil is a synthetic hydrocarbon oil or an ether synthetic oil.
  3. 　いずれも40℃における動粘度が15～350mm2/秒の非フッ素系基油およびフッ素系基油が用いられた請求項１記載の往復摺動用潤滑グリース組成物。 2. The lubricating grease composition for reciprocating sliding according to claim 1, wherein a non-fluorinated base oil and a fluorinated base oil each having a kinematic viscosity of 15 to 350 mm 2 / s at 40 ° C. are used.
  4. 　いずれも40℃における動粘度が20～300mm2/秒の非フッ素系基油およびフッ素系基油が用いられた請求項１記載の往復摺動用潤滑グリース組成物。 The lubricating grease composition for reciprocating sliding according to claim 1, wherein a non-fluorinated base oil and a fluorinated base oil each having a kinematic viscosity of 20 to 300 mm 2 / s at 40 ° C. are used.
  5. 　非フッ素系基油1～95重量％に対し、フッ素系基油が99～5重量％の割合で用いられた請求項１記載の往復摺動用潤滑グリース組成物。 The lubricating grease composition for reciprocating sliding according to claim 1, wherein the ratio of the fluorinated base oil is 99 to 5% by weight with respect to 1 to 95% by weight of the non-fluorinated base oil.
  6. 　非フッ素系基油6～89重量％に対し、フッ素系基油が94～11重量％の割合で用いられた請求項１記載の往復摺動用潤滑グリース組成物。 The lubricating grease composition for reciprocating sliding according to claim 1, wherein the fluorine-based base oil is used in a ratio of 94 to 11% by weight with respect to 6 to 89% by weight of the non-fluorinated base oil.
  7. 　非フッ素系基油1～90重量％、フッ素系基油5～80重量％、複合金属石けん0.5～30重量％およびフッ素樹脂粉末0.1～20重量％よりなり、これらの合計が100重量％である請求項５記載の往復摺動用潤滑グリース組成物。 1 to 90% by weight of a non-fluorinated base oil, 5 to 80% by weight of a fluorinated base oil, 0.5 to 30% by weight of a composite metal soap and 0.1 to 20% by weight of a fluorocarbon resin powder, and the total of these is 100% by weight A lubricating grease composition for reciprocating sliding according to claim 5.
  8. 　非フッ素系基油5～80重量％、フッ素系基油10～80重量％、複合金属石けん1～25重量％およびフッ素樹脂粉末1～15重量％よりなり、これらの合計が100重量％である請求項６記載の往復摺動用潤滑グリース組成物。 5 to 80% by weight of a non-fluorinated base oil, 10 to 80% by weight of a fluorinated base oil, 1 to 25% by weight of a composite metal soap and 1 to 15% by weight of a fluorocarbon resin powder, the total of these being 100% by weight A lubricating grease composition for reciprocating sliding according to claim 6.
  9. 　複合金属石けんがバリウム複合石けんまたはリチウム複合石けんである請求項１記載の往復摺動用潤滑グリース組成物。 The lubricating grease composition for reciprocating sliding according to claim 1, wherein the complex metal soap is a barium complex soap or a lithium complex soap.
  10. 　マイクロスイッチ用または電磁駆動弁用として用いられる請求項１記載の往復摺動用潤滑グリース組成物。 The lubricating grease composition for reciprocating sliding according to claim 1, which is used for a micro switch or a solenoid operated valve.
  11. 　マイクロスイッチまたは電磁駆動弁のアクチュエータ部位に用いられる請求項１０記載の往復摺動用潤滑グリース組成物。 11. The lubricating grease composition for reciprocating sliding according to claim 10, which is used for an actuator portion of a micro switch or an electromagnetically driven valve.
  12. 　非フッ素系基油、脂肪族ジカルボン酸およびモノアミドモノカルボン酸または脂肪族モノカルボン酸を加熱攪拌し、そこに金属水酸化物を加えて複合金属石けんを非フッ素系基油中で形成させることにより調製させた非フッ素系グリースと、フッ素系基油およびフッ素樹脂粉末から調製されたフッ素系グリースとを、混練することを特徴とする請求項１記載の往復摺動用潤滑グリース組成物の製造法。 By heating and stirring a non-fluorinated base oil, an aliphatic dicarboxylic acid and a monoamide monocarboxylic acid or an aliphatic monocarboxylic acid, and adding a metal hydroxide thereto to form a complex metal soap in the non-fluorinated base oil 2. The method for producing a lubricating grease composition for reciprocating sliding according to claim 1, wherein the prepared non-fluorinated grease and the fluorinated grease prepared from the fluorinated base oil and the fluorocarbon resin powder are kneaded.
  13. 　非フッ素系グリースとフッ素系グリースとの混練が3本ロールミルまたは高圧ホモジナイザを用いて行われる請求項１２記載の往復摺動用潤滑グリース組成物の製造法。 The method for producing a lubricating grease composition for reciprocating sliding according to claim 12, wherein the kneading of the non-fluorinated grease and the fluorinated grease is carried out using a three-roll mill or a high pressure homogenizer.
  14. 　非フッ素系基油として合成炭化水素油またはエーテル系合成油が用いられる請求項１２記載の往復摺動用潤滑グリース組成物の製造法。 The method for producing a lubricating grease composition for reciprocating sliding according to claim 12, wherein a synthetic hydrocarbon oil or an ether synthetic oil is used as the non-fluorinated base oil.
  15. 　金属水酸化物として水酸化バリウムまたは水酸化リチウムが用いられる請求項１２記載の往復摺動用潤滑グリース組成物の製造法。 The method for producing a lubricating grease composition for reciprocating sliding according to claim 12, wherein barium hydroxide or lithium hydroxide is used as the metal hydroxide.
PCT/JP2010/067744 2009-10-13 2010-10-08 Lubricating grease composition for reciprocating sliding, and manufacturing method therefor WO2011046079A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111286387A (en) * 2020-02-26 2020-06-16 上海果石实业(集团)有限公司 Damping lubricating grease for furniture sliding rail with long service life and preparation method thereof
WO2024101310A1 (en) * 2022-11-07 2024-05-16 協同油脂株式会社 Grease composition for rolling bearings, and rolling bearing

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JP2003096480A (en) * 2001-07-18 2003-04-03 Nok Kuluver Kk Lubricating grease composition
JP2006045577A (en) * 2003-04-30 2006-02-16 Ntn Corp Lubrication grease for high temperature, and rolling bearing
WO2010044386A1 (en) * 2008-10-17 2010-04-22 Ｎｏｋクリューバー株式会社 Lubricating grease composition and manufacturing method therefor

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Publication number Priority date Publication date Assignee Title
JP2003096480A (en) * 2001-07-18 2003-04-03 Nok Kuluver Kk Lubricating grease composition
JP2006045577A (en) * 2003-04-30 2006-02-16 Ntn Corp Lubrication grease for high temperature, and rolling bearing
WO2010044386A1 (en) * 2008-10-17 2010-04-22 Ｎｏｋクリューバー株式会社 Lubricating grease composition and manufacturing method therefor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111286387A (en) * 2020-02-26 2020-06-16 上海果石实业(集团)有限公司 Damping lubricating grease for furniture sliding rail with long service life and preparation method thereof
CN111286387B (en) * 2020-02-26 2022-02-01 上海果石实业(集团)有限公司 Damping lubricating grease for furniture sliding rail with long service life and preparation method thereof
WO2024101310A1 (en) * 2022-11-07 2024-05-16 協同油脂株式会社 Grease composition for rolling bearings, and rolling bearing

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