WO2010035826A1 - グリース組成物及び軸受 - Google Patents
グリース組成物及び軸受 Download PDFInfo
- Publication number
- WO2010035826A1 WO2010035826A1 PCT/JP2009/066762 JP2009066762W WO2010035826A1 WO 2010035826 A1 WO2010035826 A1 WO 2010035826A1 JP 2009066762 W JP2009066762 W JP 2009066762W WO 2010035826 A1 WO2010035826 A1 WO 2010035826A1
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- WIPO (PCT)
- Prior art keywords
- grease composition
- grease
- bearing
- metal sulfonate
- overbased metal
- Prior art date
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Classifications
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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
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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
- C10M169/06—Mixtures of thickeners and additives
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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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
- F16C33/6603—Special parts or details in view of lubrication with grease as lubricant
- F16C33/6633—Grease properties or compositions, e.g. rheological properties
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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
-
- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/10—Amides of carbonic or haloformic acids
- C10M2215/102—Ureas; Semicarbazides; Allophanates
- C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
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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
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
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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
-
- 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 and a bearing in which the same is enclosed.
- it is lubricated at high temperatures such as automobile electrical components whose lubrication points are directly connected to or near the engine that is a heating element, household electric appliances used at high speed and high temperature rotation such as cleaner motors, and continuous casting equipment.
- electrical components include alternators, electromagnetic clutches for car air conditioners, idler pulleys, intermediate pulleys, electric fan motors, fluid couplings, water pumps, distributors, and starter one-way clutches.
- the present invention relates to a grease composition having a long life that meets these lubricating conditions.
- Non-Patent Document 1 Non-Patent Document 1
- the object of the present invention is to provide a grease composition having a long life, in particular a grease composition suitable for being enclosed in a rolling bearing lubricated at high temperature, and a bearing in which the same is enclosed.
- the baking life under severe conditions such as high temperature and high speed uses a diurea compound excellent in heat resistance as a thickener, uses a base oil containing a synthetic lubricating oil, and is a well-known additive such as an antioxidant Added to extend the life.
- the inventor of the present invention has found that by adding a very small amount of a specific overbased metal sulfonate to a grease containing a diurea compound as a thickener, the oxidized and degraded product formed even under severe conditions such as high temperature and high speed for a long period of time In addition, it has been found that the curing of the grease can be suppressed, the grease can continue to flow into the lubricating portion, and the life of the grease can be significantly extended, and the present invention has been completed.
- the present invention provides the following grease composition. 1.
- a grease composition comprising a base oil, a urea thickener and an additive
- the additive contains an overbased metal sulfonate;
- a grease composition characterized in that the content of the overbased metal sulfonate is 0.05 to 1.00% by mass with respect to the total amount of the grease composition. 2.
- the present invention by adding a very small amount of a specific overbased metal sulfonate to a grease containing a diurea compound as a thickener, it is possible to capture the oxidized deterioration product even under severe conditions such as high temperature and high speed for a long time As a result, the curing of the grease can be suppressed, the grease can continue to flow into the lubricating portion, and the life of the grease can be significantly extended.
- Examples of the metal of the overbased metal sulfonate used in the present invention include Ca, Na, Ba, Li, Zn, Pb, Mg and the like, and preferable ones are Ca, Na, Mg and the like.
- Particularly preferred is an overbased Ca sulfonate in which fine particles of metal carbonates such as CaCO 3 and Ca (OH) 2 and metal hydroxides are dispersed in a base oil.
- the overbased metal sulfonate used in the present invention is generally used as a detergent / dispersant for engine oil etc., and in greases, it is usually used for the purpose of improving rust resistance, extreme pressure resistance and peel resistance. .
- the amount of use of the overbased metal sulfonate is much more than that used in the above conventional purposes (for example, JP-A-2002-53884 and JP-A-2003-321694). Small amount.
- the content of the overbased metal sulfonate in the grease composition of the present invention is 0.05 to 1.00% by mass, preferably 0.08 to 0.70% by mass, particularly preferably 0.10 to 0.40. It is mass%. If the amount is less than 0.05% by mass, the effect is insufficient. If the amount is more than 1.00% by mass, the oxidative deterioration of the base oil is promoted, and the baking life is reduced.
- base oils including mineral oil
- ester-based synthetic oils represented by diesters and polyol esters
- synthetic hydrocarbon oils represented by poly- ⁇ -olefins and polybutenes
- ether-based synthetic oils represented by alkyldiphenyl ether and polypropylene glycol
- silicone oils fluorinated oils, etc.
- synthetic oils can be used, and these may be used alone or in combination of two or more.
- the urea thickeners used in the present invention include all urea thickeners represented by diurea. Among them, particularly preferred diurea thickeners are those represented by the following formula (1).
- R 1 NH-CO-NH-R 3 -NH-CO-NHR 2 are the same or different and are an alkyl group having 6 to 30 carbon atoms, an aryl group having 6 or 7 carbon atoms, or a cyclohexyl group.
- R 3 is a divalent organic radical, e.g., -C 6 H 4 -CH 2 -C 6 H 4 -, -C 6 H 4 -, - C 6 H 3 (CH 3) - shows the like.
- Such diurea-based thickeners include alkylmonoamines such as octylamine, stearylamine, dodecylamine and hexadecylamine, arylmonoamines such as aniline and p-toluidine, monoamines such as cyclohexylamine and diphenylmethane-4,4'- It is obtained by the reaction with diisocyanates such as diisocyanate, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
- Particularly preferred thickeners are alkyl or cyclohexyl groups having 6 to 30 carbon atoms in which R 1 and R 2 are the same or different, and R 3 is —C 6 H 4 —CH 2 —C 6 H 4 — Or a diurea compound of the formula (1) which is —C 6 H 3 (CH 3 ) —.
- the content of the urea thickener in the grease composition of the present invention is preferably 3 to 20% by mass, more preferably 4 to 15% by mass, based on the total weight of the grease composition.
- Phenols 2,6-di-tert-butyl-p-cresol, pentaerythrityl tetrakis [3- (3, 5 Hindered phenols such as -di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like; quinoline system; 2, 2, 4- Trimethyl-1,2 dihydroquinoline polymer etc.
- Rust inhibitor carboxylic acid and derivatives thereof alkenyl succinic anhydride, alkenyl succinic acid ester, alkenyl succinic acid half ester carboxylate salt; fatty acid, dibasic acid, naphthenic acid, lanolin fatty acid, metal such as alkenyl succinic acid (Ca, Ba, Mg, Al, Zn, Na etc.) or amine salts Sulfonates; Ba salts of sulfonic acids, Ca salts, Zn salts, Na salts etc. Passivators; Na nitrites, Na molybdates etc. esters; sorbitan trio , Sorbitan monooleate, etc. Metal corrosion inhibitors; benzotriazole or derivatives thereof, zinc oxide etc.
- Extreme pressure agent Phosphorus compound; Tricresyl phosphate, tri-2-ethylhexyl phosphate, etc.
- Sulfur compound Dibenzyldisulfide, various polysulfides, etc .: Sulfur-phosphorus compound; Triphenyl phosphorothioate, organometalic extreme pressure agent Salts of dialkyl dithiophosphoric acid such as Zn, Mo, Sb, Bi, etc., salts of dialkyl dithiocarbamic acid such as Zn, Mo, Sb, Ni, Cu, Bi, etc. and others, ashless dithiocarbamate, ashless dithiophosphate carbamate etc.
- Solid lubricants Molybdenum disulfide, graphite, PTFE, MCA etc.
- the base oil is oxidized and degraded under severe conditions such as high temperature and high speed for a long period of time, the grease is hardened by the interaction between the oxidized degradation product and the urea thickener, and the influx into the lubricating portion Cause burn-in.
- the overbased metal sulfonate since a trace amount of the overbased metal sulfonate is added, this can capture the oxidized deterioration product of the urea grease, suppress the hardening of the grease, and can keep the grease flowing into the lubrication part, and the life is shortened. It can be extended.
- Base grease A Thickener Aromatic diurea (reactant of tolylene diisocyanate and paratoluidine)
- Base oil alkyl diphenyl ether oil (Matsumura Oil Research Institute Co., Ltd .: Moresco High Lub LB-100)
- Toughness 300 ⁇
- Base oil alkyl diphenyl ether oil (Matsumura Oil Research Institute Co., Ltd .: Moresco High Lub LB-100)
- Base grease C Thickener: Aromatic diurea (reactant of tolylene diisocyanate and paratoluidine)
- Base oil Poly alpha olefin oil (manufact
- Baking life test method (ASTM D 3336 mod.)
- the greases of Examples 1 to 6 of the present invention use a urea compound as a thickening agent and contain a trace amount of overbased metal sulfonate, so that greases (Comparative Examples 1, 4 and 5) and non-added greases are used. In comparison, the bake life is extremely long. The addition effect of the overbased metal sulfonate is remarkable in the urea-based grease. That is, in Comparative Example 6 in which the thickener was replaced with Li soap in Example 2, the additive addition effect was not at all.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Lubricants (AREA)
- Rolling Contact Bearings (AREA)
Abstract
Description
電装品の代表例としては、オルタネータ、カーエアコン用電磁クラッチ、アイドラプーリ、中間プーリ、電動ファンモータ、流体継手、水ポンプ、ディストリビュータ、スタータワンウエイクラッチなどがある。本発明は、これらの潤滑条件に応える長寿命を有するグリース組成物に関する。
例えば、高温・高速軸受用グリース組成物として、増ちょう剤にジウレア化合物を、基油にアルキルジフェニルエーテル油を用いたグリースが、自動車電装部品、エンジン補機等用のグリースとして提案されている(特許文献1~4など)。
また、基油にエステル油を10質量%以上含有させることにより、高温高速における早期焼付きを抑えたグリースもあるが、必ずしも満足できる性能を有していなかった。
グリースの酸化防止性を向上する為の添加剤の中では、酸化防止剤以外の添加剤の使用例は無い。しかし、酸化防止剤の酸化防止効果には、必然的に油との相互作用が伴い、酸化安定性に対する要求は油自体の要求ともなる。従って、油の種類が一定である限り自ら限度があり、その酸化防止機構から考えて酸化防止剤を単独で使用することにより酸化防止効果を飛躍的に向上させることは期待できない(非特許文献1)。
基油、増ちょう剤及び酸化防止剤として新規なものは少なく、これ以上の改善は難しいのが現状である。
本発明者は、ジウレア化合物を増ちょう剤とするグリースに極少量の特定の過塩基性金属スルホネートを添加することにより、長期間の高温、高速等の厳しい条件においても、生成した酸化劣化物を補足し、グリースの硬化を抑え、潤滑部へグリースを流入し続けることができ、グリースの寿命を顕著に延長することが出来ることを見出し本発明を完成するに至った。
本発明は下記のグリース組成物を提供するものである。
1.基油、ウレア系増ちょう剤、及び添加剤を含むグリース組成物において、
該添加剤が、過塩基性金属スルホネートを含有すること、
該過塩基性金属スルホネートの含有量が、グリース組成物の全量に対して、0.05-1.00質量%であることを特徴とするグリース組成物。
2.過塩基性金属スルホネートのTBNが、50~500mgKOH/gであることを特徴とする上記1記載のグリース組成物。
3.上記1又は2記載のグリース組成物を封入した軸受。
過去にCaCO3やCa(OH)2などの金属炭酸塩や金属水酸化物のほか金属炭酸塩や金属水酸化物の微粒子等を分散させた過塩基性金属スルホネートを極く少量使用した場合に、グリースの寿命を延長する旨の報告・開示は全く知られていない。
0.05質量%未満では効果が不充分であり、1.00質量%を越えて添加すると基油の酸化劣化が促進され、逆に焼付寿命が低下してしまう。
(1) R1NH-CO-NH-R3-NH-CO-NHR2
式中、R1及びR2 は同一もしくは異なる、炭素原子数6~30のアルキル基、炭素原子数6又は7のアリール基もしくはシクロヘキシル基である。R3は、2価の有機基、例えば、-C6H4-CH2-C6H4-、
-C6H4-、-C6H3(CH3)-等を示す。
このようなジウレア系増ちょう剤は、オクチルアミン、ステアリルアミン、ドデシルアミン、ヘキサデシルアミン等のアルキルモノアミン、アニリン、p-トルイジン等のアリールモノアミン、シクロヘキシルアミン等のモノアミンとジフェニルメタン-4、4'-ジイソシアネート、2,4-トリレン-ジイソシアネート、2,6-トリレン-ジイソシアネート等のジイソシアネートとの反応によって得られる。特に好ましい増ちょう剤は、R1及びR2が同一もしくは異なる、炭素原子数6~30のアルキル基もしくはシクロヘキシル基であり、R3が、-C6H4-CH2-C6H4-、又は-C6H3(CH3)-である式(1)のジウレア系化合物である。
本発明のグリース組成物中のウレア系増ちょう剤の含有量は、グリース組成物全体に対して好ましくは3~20質量%、さらに好ましくは4~15質量%である。
・酸化防止剤
アミン類;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、アルキル化ジフェニルアミンなど
フェノール類;2、6-ジ-tert-ブチル-p-クレゾール、ペンタエリスリチル・テトラキス[3-(3、5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、オクタデシル-3-(3、5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネートなどのヒンダードフェノール
キノリン系;2、2、4-トリメチル-1、2ジヒドロキノリン重合体など
カルボン酸およびその誘導体;アルケニルコハク酸無水物、アルケニルコハク酸エステル、アルケニルコハク酸ハーフエステル
カルボン酸塩;脂肪酸、二塩基酸、ナフテン酸、ラノリン脂肪酸、アルケニルコハク酸などの金属(Ca、Ba、Mg、Al、Zn、Naなど)又はアミン塩
スルホン酸塩;スルホン酸のBa塩、Ca塩、Zn塩、Na塩など
不働態化剤;亜硝酸Na、モリブデン酸Naなど
エステル;ソルビタントリオレート、ソルビタンモノオレートなど
金属腐食防止剤;ベンゾトリアゾール又はその誘導体、酸化亜鉛など
リン系化合物;トリクレジルホスフェート、トリ-2-エチルヘキシルホスフェートなど 硫黄系化合物;ジベンジルジサルファイド、各種ポリサルファイドなど
硫黄-リン系化合物;トリフェニールホスホロチオネート
有機金属系極圧剤;ジアルキルジチオリン酸のZn、Mo、Sb、Biなどの塩、ジアルキルジチオカルバミン酸のZn、Mo、Sb、Ni、Cu、Biなどの塩など
その他、無灰ジチオカーバメート、無灰ジチオフォスフェートカーバメートなど
・固体潤滑剤;二硫化モリブデン、グラファイト、PTFE、MCAなど。
本発明では、過塩基性の金属スルホネートを微量添加しているため、これが、ウレアグリースの酸化劣化物を補足し、グリースの硬化を抑え、潤滑部へグリースを流入し続けることができ、寿命を延長することができる。
実施例、比較例に示すベースグリースに、添加剤を加えよく混ぜ、3本ロールミルで混練した。
・ベースグリースA
増ちょう剤:芳香族ジウレア(トリレンジイソシアネートとパラトルイジンとの反応物)
基油:アルキルジフェニルエーテル油(株式会社松村石油研究所製:モレスコハイルーブLB-100)
混和ちょう度:300
・ベースグリースB
増ちょう剤:脂肪族ジウレア(ジフェニルメタン‐4、4´-ジイソシアネートとオクチルアミンとの反応物)
基油:アルキルジフェニルエーテル油(株式会社松村石油研究所製:モレスコハイルーブLB-100)
混和ちょう度:300
・ベースグリースC
増ちょう剤:芳香族ジウレア(トリレンジイソシアネートとパラトルイジンとの反応物)
基油:ポリαオレフィン油(エクソンモービル化学製:MOBIL SHF-101) 混和ちょう度:300
・ベースグリースD
増ちょう剤:ステアリン酸リチウム
基油:ポリαオレフィン油(エクソンモービル化学製:MOBIL SHF-101) 混和ちょう度:300
過塩基性Caスルホネート(Crompton製:BRYTON C-400C(TBN405))
過塩基性Mgスルホネート(Crompton製:BRYTON M-400TG(TBN395))
過塩基性Naスルホネート(Lubrizol製:Lubrizol5318(TBN448))
軸受6204に試験グリースを1.8g充填して、両側に鋼板のシールド板を加締め、その軸受の外輪温度を180℃に保ち、荷重Fa=Fr=67Nの条件下、10000rpmで内輪を連続運転させる。軸受の回転トルクが過大になり、過電流(4アンペア)を生じるまで、または軸受温度が15℃以上上昇するまでの時間を焼付寿命とした。
結果をその組成とともに表1及び表2に示す。
過塩基性金属スルホネートの添加効果はウレア系グリースにおいて顕著である。すなわち、実施例2において増ちょう剤をLi石けんに代えた比較例6では添加剤の添加効果が全く無い。
また、過塩基性金属スルホネートの添加量が0.02質量%の比較例2、5.00質量%の比較例3でも本発明の焼付寿命延長効果は奏されないことがわかる。
Claims (3)
- 基油、ウレア系増ちょう剤、及び添加剤を含むグリース組成物において、
該添加剤が、過塩基性金属スルホネートを含有すること、
該過塩基性金属スルホネートの含有量が、グリース組成物の全量に対して、0.05-1.00質量%であることを特徴とするグリース組成物。 - 過塩基性金属スルホネートのTBNが、50~500mgKOH/gであることを特徴とする請求項1記載のグリース組成物。
- 請求項1又は2記載のグリース組成物を封入した軸受。
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JPWO2013031705A1 (ja) * | 2011-08-26 | 2015-03-23 | 日本精工株式会社 | グリース組成物及び転動装置 |
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JP6739951B2 (ja) * | 2016-03-11 | 2020-08-12 | 株式会社デンソー | グリース組成物、機械部材及びスタータオーバーランニングクラッチ |
JP6845633B2 (ja) | 2016-08-04 | 2021-03-17 | 協同油脂株式会社 | グリース組成物 |
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