JP2013147548A - Grease composition and bearing - Google Patents

Grease composition and bearing Download PDF

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JP2013147548A
JP2013147548A JP2012008027A JP2012008027A JP2013147548A JP 2013147548 A JP2013147548 A JP 2013147548A JP 2012008027 A JP2012008027 A JP 2012008027A JP 2012008027 A JP2012008027 A JP 2012008027A JP 2013147548 A JP2013147548 A JP 2013147548A
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grease composition
mass
bearing
thickener
formula
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JP5872300B2 (en
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Osamu Saida
理 齊田
Yuji Onuki
裕次 大貫
Masamichi Yamamoto
正道 山本
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Kyodo Yushi Co Ltd
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Kyodo Yushi Co Ltd
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Priority to JP2012008027A priority Critical patent/JP5872300B2/en
Priority to US14/363,913 priority patent/US20140336090A1/en
Priority to DE112013000604.9T priority patent/DE112013000604B4/en
Priority to CN201380005510.1A priority patent/CN104053757A/en
Priority to PCT/JP2013/050968 priority patent/WO2013108887A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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    • C10M169/00Lubricating 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
    • C10M169/06Mixtures of thickeners and additives
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30Parts of ball or roller bearings
    • F16C33/66Special parts or details in view of lubrication
    • F16C33/6603Special parts or details in view of lubrication with grease as lubricant
    • F16C33/6633Grease properties or compositions, e.g. rheological properties
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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    • C10M2207/125Carboxylix 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
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Lubricants (AREA)
  • Rolling Contact Bearings (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a grease composition which is suitably used for a rolling bearing which is under high temperatures, and shows stable lubricity for a long period, and to provide a bearing including the same.SOLUTION: A grease composition includes: (a) a base oil; (b) a thickener; (c) a compound represented by formula (1) and having alkylthiocarbamoyl group; (d) a hindered phenol antioxidant; and (e) a metal deactivator (In the formula, each of R, R, Rand Rindependently represents 1-20C alkyl; and X represents S, S-S, S-CH-S, S-CHCH-S or S-CHCHCH-S).

Description

本発明は、基油、増ちょう剤、特定の酸化防止剤及び金属不活性化剤を含有するグリース組成物に関する。詳しくは、高温条件にある転がり軸受に使用するのに好適な、潤滑寿命を向上したグリース組成物、及びこれを封入した軸受に関する。   The present invention relates to a grease composition containing a base oil, a thickener, a specific antioxidant and a metal deactivator. Specifically, the present invention relates to a grease composition with an improved lubrication life suitable for use in a rolling bearing under a high temperature condition, and a bearing in which the grease composition is enclosed.

鉄道車両、自動車、電機、各種産業機械などに使用されるモータは、近年の高速化や省エネ化、低騒音化、省保守化の要望により、小型・軽量化、高回転化、高効率化、長寿命化が進められている。小型・軽量化に伴い、潤滑剤の使用量は減少し、また高回転化による使用温度の上昇など、潤滑剤の使用環境は厳しくなってきている。特に鉄道車両用主電動機では、騒音問題や保守周期延長の要求から、モータの全閉化が進められているが、従来の開放型に比べ冷却効率が悪くなることから、更なる耐熱・長寿命グリースが必要とされている。   Motors used in railway vehicles, automobiles, electrical machinery, various industrial machines, etc. have become smaller, lighter, faster, and more efficient due to recent demands for higher speeds, energy savings, noise reduction, and maintenance. Longevity is being promoted. With the reduction in size and weight, the amount of lubricant used has decreased, and the environment in which the lubricant is used has become severe, such as an increase in operating temperature due to higher rotation. In particular, in the main motors for railway vehicles, the motors are being fully closed due to noise problems and requests for extended maintenance cycles. However, the cooling efficiency is worse than that of the conventional open type. Grease is needed.

これまでに、グリース組成物の性能向上に関する種々の提案がされている。
基油、増ちょう剤にアルキルチオカルバモイル基を有する化合物、およびアミン−ケトン縮合物系酸化防止剤を含有することにより、高温条件での転がり軸受の潤滑寿命を向上させたグリースが提案されている(特許文献1)。
潤滑基材に、アルキルチオカルバモイル基を有する化合物及びモリブデン化合物を添加し、あるいはさらにエステル化合物を添加することにより疲労寿命を改良した疲労寿命改良潤滑剤が提案されている(例えば、特許文献2参照)。
また、(a)メチレンビス(ジ‐n‐ブチルジチオカルバメート)及び(b)トルトリアゾール又はベンゾトリアゾールのジフェニルアミン誘導体から成り、(a):(b)質量%比が約4:1〜約50:1の範囲である改良された抗酸化性の抗磨耗性極圧組成物及びそれを含む潤滑剤が提案されている(例えば、特許文献3参照)。
さらに、(a)潤滑油、(b)少なくとも1個のヒドロキシル基を含む炭素数12〜24の脂肪族モノカルボン酸のリチウム塩、炭素数2〜12の脂肪族ジカルボン酸の二リチウム塩、及び炭素数12〜24の脂肪族モノカルボン酸のリチウム塩からなる群から選ばれる少なくとも1種の化合物、及び(c)3‐(N‐サリチロイル)アミノ‐1,2,4‐トリアゾール及びデカメチレン‐ジカルボキシリックアシッド‐ジサリチロイルヒドラジドからなる群から選ばれる少なくとも1種の化合物を含有するリチウムグリース組成物が提案されている(例えば、特許文献4参照)。
しかし、これらの添加剤を使用したグリース組成物を高温条件にある転がり軸受に利用しても、熱酸化安定性及び潤滑寿命が不十分であり、ユーザーの満足するものは未だ得られていないのが現状である。
So far, various proposals for improving the performance of grease compositions have been made.
A grease that improves the lubrication life of a rolling bearing under high-temperature conditions by containing a base oil, a compound having an alkylthiocarbamoyl group in a thickener, and an amine-ketone condensate antioxidant has been proposed ( Patent Document 1).
There has been proposed a fatigue life improving lubricant in which a fatigue life is improved by adding a compound having an alkylthiocarbamoyl group and a molybdenum compound to a lubricating base material, or further adding an ester compound (see, for example, Patent Document 2). .
And (a) methylenebis (di-n-butyldithiocarbamate) and (b) a diphenylamine derivative of toltriazole or benzotriazole, wherein the (a) :( b) mass% ratio is about 4: 1 to about 50: 1. An improved antioxidative antiwear extreme pressure composition and a lubricant containing the same have been proposed (see, for example, Patent Document 3).
Furthermore, (a) a lubricating oil, (b) a lithium salt of an aliphatic monocarboxylic acid having 12 to 24 carbon atoms containing at least one hydroxyl group, a dilithium salt of an aliphatic dicarboxylic acid having 2 to 12 carbon atoms, and At least one compound selected from the group consisting of lithium salts of aliphatic monocarboxylic acids having 12 to 24 carbon atoms, and (c) 3- (N-salicyloyl) amino-1,2,4-triazole and decamethylene-di A lithium grease composition containing at least one compound selected from the group consisting of carboxylic acid-disalicyloyl hydrazide has been proposed (see, for example, Patent Document 4).
However, even if a grease composition using these additives is used for a rolling bearing under a high temperature condition, the thermal oxidation stability and the lubrication life are insufficient, and a product satisfying the user has not yet been obtained. Is the current situation.

特開2007−238755号公報JP 2007-238755 A 特公平03−31760号公報Japanese Patent Publication No. 03-31760 特表2005−509732号公報JP 2005-509732 A 特許第2936084号Japanese Patent No. 2936084

熱酸化安定性に優れるグリースとしては、分子内に金属を含まないウレア化合物を増ちょう剤とし、合成油を基油としたグリースが、深溝玉軸受を主に使用する自動車の電装補機に一般的に使用されているが、円筒ころ軸受を必須とする鉄道車両用主電動機に適用した場合は、十分な潤滑寿命を得ることが出来ない。
本発明の目的は、高温条件にある転がり軸受に好適であり、また安定した潤滑性を長期間示すグリース組成物を提供することである。即ち、熱酸化安定性及び潤滑寿命に優れているグリース組成物を提供することである。
本発明の他の目的は、上記グリース組成物を封入した軸受を提供することである。
As a grease with excellent thermal oxidation stability, a grease containing a urea compound that does not contain metal in the molecule as a thickener and a synthetic oil as a base oil is commonly used in electrical accessories for automobiles that mainly use deep groove ball bearings. However, when applied to a railway vehicle main motor that requires a cylindrical roller bearing, a sufficient lubrication life cannot be obtained.
An object of the present invention is to provide a grease composition that is suitable for a rolling bearing under a high temperature condition and that exhibits stable lubricity for a long period of time. That is, to provide a grease composition having excellent thermal oxidation stability and lubrication life.
Another object of the present invention is to provide a bearing in which the grease composition is enclosed.

本発明者らは上記目的を達成するために鋭意研究の結果、基油、増ちょう剤、特定の酸化防止剤、さらに金属不活性化剤を用いることにより、熱酸化安定性及び潤滑寿命を改善し、高温下にある転がり軸受に好適であり、また安定した潤滑性を長期間示すグリース組成物を完成させた。   As a result of diligent research, the present inventors have improved the thermal oxidation stability and lubrication life by using a base oil, a thickener, a specific antioxidant, and a metal deactivator. Thus, a grease composition suitable for a rolling bearing at a high temperature and having a stable lubricity for a long time was completed.

本発明は以下に示すグリース組成物及び軸受を提供するものである。
〔1〕(a)基油、(b)増ちょう剤、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物、(d)ヒンダードフェノール系酸化防止剤、及び(e)金属不活性化剤を含有することを特徴とするグリース組成物。
The present invention provides the following grease composition and bearing.
[1] (a) base oil, (b) thickener, (c) compound having alkylthiocarbamoyl group represented by formula (1), (d) hindered phenol antioxidant, and (e) metal A grease composition comprising an inactivating agent.

Figure 2013147548
Figure 2013147548

(式中、R1、R2、R3、R4は独立して炭素数1〜20のアルキル基を示し、Xは、S、S−S、S−CH2−S、S−CH2CH2−S又はS−CH2CH2CH2−Sを示す。)
〔2〕(d)ヒンダードフェノール系酸化防止剤が、2, 6-ジ-tert-ブチル-4-メチルフェノールである〔1〕記載のグリース組成物。
〔3〕(e)金属不活性化剤が、デカメチレンカルボン酸ジサリチロイルヒドラジドである〔1〕又は〔2〕に記載のグリース組成物。
〔4〕(a)基油が、ポリオールエステル油とアルキルジフェニルエーテル油との混合油である〔1〕〜〔3〕のいずれかに記載のグリース組成物。
〔5〕(b)増ちょう剤が、リチウム石けん及び複合リチウム石けんからなる群から選ばれる少なくとも1種である〔1〕〜〔4〕のいずれかに記載のグリース組成物。
〔6〕グリース組成物全体に対して、(a)基油50質量%以上、(b)増ちょう剤1〜30質量%、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物0.1〜10質量%、(d)ヒンダードフェノール系酸化防止剤0.1〜10質量%、(e)金属不活性0.1〜10質量%を含有する〔1〕〜〔5〕のいずれかに記載のグリース組成物。
〔7〕〔1〕〜〔6〕のいずれかに記載のグリース組成物を封入した軸受。
(In the formula, R 1 , R 2 , R 3 and R 4 independently represent an alkyl group having 1 to 20 carbon atoms, and X represents S, S—S, S—CH 2 —S, S—CH 2. It shows a CH 2 -S or S-CH 2 CH 2 CH 2 -S.)
[2] The grease composition according to [1], wherein (d) the hindered phenol antioxidant is 2,6-di-tert-butyl-4-methylphenol.
[3] The grease composition according to [1] or [2], wherein (e) the metal deactivator is decamethylene carboxylic acid disalicyloyl hydrazide.
[4] The grease composition according to any one of [1] to [3], wherein (a) the base oil is a mixed oil of a polyol ester oil and an alkyl diphenyl ether oil.
[5] The grease composition according to any one of [1] to [4], wherein (b) the thickener is at least one selected from the group consisting of lithium soap and composite lithium soap.
[6] Compound having an alkylthiocarbamoyl group represented by (a) 50% by mass or more of base oil, (b) 1 to 30% by mass of thickener, and (c) formula (1) with respect to the entire grease composition. [1] to [5] containing 0.1 to 10% by mass, (d) 0.1 to 10% by mass of a hindered phenol antioxidant, and (e) 0.1 to 10% by mass of a metal inert. The grease composition according to any one of the above.
[7] A bearing in which the grease composition according to any one of [1] to [6] is enclosed.

本発明のグリース組成物は、改善された熱酸化安定性及び潤滑寿命を有し、高温条件にある転がり軸受に使用するのに好適であり、また安定した潤滑性を長期間示すため、非常に有用である。本発明のグリース組成物はまた、高温で使用しても長期間にわたって一定のちょう度を保ち、著しく硬化したり軟化したりすることがない。   The grease composition of the present invention has improved thermal oxidation stability and lubrication life, is suitable for use in rolling bearings under high temperature conditions, and exhibits stable lubricity for a long time. Useful. The grease composition of the present invention also maintains a constant consistency over a long period of time even when used at high temperatures, and does not harden or soften significantly.

(a)基油
本発明のグリース組成物の基油としては、鉱油、合成油及びこれらの混合油を使用することができる。合成油としては、ジエステル、ポリオールエステルに代表されるエステル系合成油、ポリ−α−オレフィン、ポリブテンに代表される合成炭化水素油、アルキルジフェニルエーテル、ポリプロピレングリコールに代表されるエーテル系合成油、シリコーン油、フッ素化油などがあげられる。
本発明では、混合油を使用するのが好ましく、2種以上の合成油の混合油がより好ましく、エステル系合成油の混合油が更に好ましく、特に耐熱性に優れるポリオールエステル系合成油とアルキルジフェニルエーテル系合成油との混合油であることが好ましい。
基油の40℃における動粘度が、30〜300mm2/sであるのが好ましい。40℃の動粘度が30mm2/sを下回ると、蒸発量の増加及び油膜厚さの減少による潤滑性の低下により長寿命が望めないので好ましくない。一方、40℃の動粘度が300mm2/sを上回ると、粘性抵抗が増大し、トルク上昇を引き起こすので好ましくない。
本発明のグリース組成物は、グリース組成物全体に対して、(a)基油を、好ましくは50質量%以上、より好ましくは60質量%以上含有する。
(A) Base oil Mineral oil, synthetic oil, and mixed oils thereof can be used as the base oil of the grease composition of the present invention. Synthetic oils include diesters, ester-based synthetic oils represented by polyol esters, poly-α-olefins, synthetic hydrocarbon oils represented by polybutene, alkyl diphenyl ethers, ether-based synthetic oils represented by polypropylene glycol, and silicone oils. And fluorinated oils.
In the present invention, a mixed oil is preferably used, a mixed oil of two or more kinds of synthetic oils is more preferable, a mixed oil of ester-based synthetic oils is more preferable, and a polyol ester-based synthetic oil and an alkyl diphenyl ether particularly excellent in heat resistance. It is preferably a mixed oil with a synthetic oil.
The base oil preferably has a kinematic viscosity at 40 ° C. of 30 to 300 mm 2 / s. If the kinematic viscosity at 40 ° C. is less than 30 mm 2 / s, it is not preferable because a long life cannot be expected due to a decrease in lubricity due to an increase in evaporation amount and a decrease in oil film thickness. On the other hand, if the kinematic viscosity at 40 ° C. exceeds 300 mm 2 / s, the viscous resistance increases, causing an increase in torque, which is not preferable.
The grease composition of the present invention contains (a) a base oil, preferably 50% by mass or more, more preferably 60% by mass or more, based on the entire grease composition.

(b)増ちょう剤
本発明のグリース組成物の増ちょう剤としては、全ての増ちょう剤が使用可能である。具体的には、リチウム石けんや複合リチウム石けんに代表される石けん系増ちょう剤、ジウレアに代表されるウレア系増ちょう剤、有機化クレイやシリカに代表される無機系増ちょう剤、PTFEに代表される有機系増ちょう剤などがあげられる。
本発明において使用可能な複合リチウム石けんとしては、1個以上のヒドロキシル基を有する炭素数12〜24のヒドロキシ脂肪酸と、炭素数2〜12の脂肪酸ジカルボン酸のリチウム塩とから構成されるものが好ましい。前記ヒドロキシ脂肪酸としては、12−ヒドロキシステアリン酸、12−ヒドロキシラウリン酸、16−ヒドロキシパルミチン酸等が挙げられる。このうち、12−ヒドロキシステアリン酸が好ましい。前記脂肪族ジカルボン酸としては、アゼライン酸、セバシン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スペリン酸、ウンデカン二酸、ドデカン二酸が挙げられる。アゼライン酸が最も好ましい。
(B) Thickener As the thickener of the grease composition of the present invention, all thickeners can be used. Specifically, soap thickeners represented by lithium soap and composite lithium soap, urea thickeners represented by diurea, inorganic thickeners represented by organoclay and silica, and representative PTFE. And organic thickeners.
The composite lithium soap usable in the present invention is preferably composed of a hydroxy fatty acid having 12 to 24 carbon atoms having one or more hydroxyl groups and a lithium salt of a fatty acid dicarboxylic acid having 2 to 12 carbon atoms. . Examples of the hydroxy fatty acid include 12-hydroxystearic acid, 12-hydroxylauric acid, and 16-hydroxypalmitic acid. Of these, 12-hydroxystearic acid is preferred. Examples of the aliphatic dicarboxylic acid include azelaic acid, sebacic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, undecanedioic acid, and dodecanedioic acid. Azelaic acid is most preferred.

本発明で使用する増ちょう剤としては、石けん系増ちょう剤が好ましく、リチウム石けん及び複合リチウム石けんが耐熱性に優れるためより好ましい。複合リチウム石けんの中でも、12−ヒドロキシステアリン酸と、アゼライン酸のリチウム塩が最も好ましい。リチウム石けん及び複合リチウム石けんは、円筒ころ軸受を必須とする主電動機へ適用した場合にも、ウレア化合物よりも長い潤滑寿命を得ることが出来るため好ましい。
本発明のグリース組成物は、グリース組成物全体に対して、(b)増ちょう剤を、好ましくは1〜30質量%、より好ましくは5〜20質量%を含有する。増ちょう剤量が多すぎると、グリースが硬くなり撹拌抵抗が大きくなる可能性がある。逆に増ちょう剤量が少なすぎると、グリースが軟化し漏洩する可能性がある。
As the thickener used in the present invention, a soap-based thickener is preferable, and lithium soap and composite lithium soap are more preferable because of excellent heat resistance. Of the composite lithium soaps, 12-hydroxystearic acid and the lithium salt of azelaic acid are most preferred. Lithium soap and composite lithium soap are preferable because they can provide a longer lubrication life than urea compounds when applied to a main motor that requires a cylindrical roller bearing.
The grease composition of the present invention contains (b) a thickener, preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the entire grease composition. If the amount of the thickener is too large, the grease becomes hard and the stirring resistance may increase. Conversely, if the amount of thickener is too small, the grease may soften and leak.

添加剤
本発明のグリース組成物は、酸化防止剤として、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物(ATC)及び(d)ヒンダードフェノール系酸化防止剤を含有する。本発明のグリース組成物は更に(e)金属不活性化剤を含有する。
Additive The grease composition of the present invention contains (c) a compound (ATC) having an alkylthiocarbamoyl group represented by the formula (1) and (d) a hindered phenol antioxidant as antioxidants. The grease composition of the present invention further contains (e) a metal deactivator.

(c)本発明で使用するアルキルチオカルバモイル基を有する化合物は、下記式(1)で表される。   (C) The compound having an alkylthiocarbamoyl group used in the present invention is represented by the following formula (1).

Figure 2013147548
Figure 2013147548

式(1)中、R1、R2、R3、R4は独立して炭素数1〜20の直鎖又は分岐アルキル基、好ましくは炭素数1〜8の直鎖又は分岐アルキル基を示す。R1〜R4が全て同じ基であるのが好ましい。
Xは、S、S−S、S−CH2−S、S−CH2CH2−S又はS−CH2CH2CH2−Sを示す。このうち、S−CH2−Sが好ましい。
式(1)で表される化合物としては、ビス(ジメチルチオカルバモイル)モノスルフィド、ビス(ジメチルカルバモイル)ジスルフィド、メチレンビス(ジメチルジチオカーバメート)、メチレンビス(ジーn−ブチルジチオカーバメート)等があげられる。このうち、メチレンビス(ジーn−ブチルジチオカーバメート)が好ましい。
本発明のグリース組成物は、グリース組成物全体に対して、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物を、好ましくは0.1〜10質量%、より好ましくは0.5〜5質量%含有する。(c)の量が10質量%を超えると、酸化劣化防止効果が飽和し、(c)の量が0.1質量%未満であると、添加の効果が得られない。
In the formula (1), R 1 , R 2 , R 3 and R 4 independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms. . R 1 to R 4 are preferably all the same group.
X represents S, S—S, S—CH 2 —S, S—CH 2 CH 2 —S or S—CH 2 CH 2 CH 2 —S. Among, S-CH 2 -S are preferred.
Examples of the compound represented by the formula (1) include bis (dimethylthiocarbamoyl) monosulfide, bis (dimethylcarbamoyl) disulfide, methylenebis (dimethyldithiocarbamate), methylenebis (di-n-butyldithiocarbamate), and the like. Of these, methylenebis (di-n-butyldithiocarbamate) is preferred.
In the grease composition of the present invention, the compound having an alkylthiocarbamoyl group represented by the formula (1) (c) is preferably 0.1 to 10% by mass, more preferably 0.8%, based on the entire grease composition. 5 to 5% by mass is contained. When the amount of (c) exceeds 10% by mass, the effect of preventing oxidative degradation is saturated, and when the amount of (c) is less than 0.1% by mass, the effect of addition cannot be obtained.

(d)ヒンダードフェノール系酸化防止剤としては、2, 6-ジ-tert-ブチル-4-メチルフェノール、ペンタエリスリトールテトラキス(3-(3, 5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート)、ベンゼンプロパン酸, 3, 5-ビス(1, 1-ジメチル-エチル)-4-ヒドロキシC7-C9側鎖アルキルエステル、及びオクタデシル-3-(3, 5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネートからなる群から選ばれる1種以上などがあげられる。このうち、2, 6-ジ-tert-ブチル-4-メチルフェノールが好ましい。
本発明のグリース組成物は、グリース組成物全体に対して、(d)ヒンダードフェノール系酸化防止剤を、好ましくは0.1〜10質量%、より好ましくは0.5〜5質量%含有する。(d)の量が10質量%を超えると、酸化劣化防止が飽和し、(d)の量が0.1質量%未満であると、添加の効果が得られない。
(D) Examples of hindered phenol antioxidants include 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate), benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy C7-C9 side chain alkyl ester, and octadecyl-3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate and one or more selected from the group consisting of propionate. Of these, 2,6-di-tert-butyl-4-methylphenol is preferred.
The grease composition of the present invention contains (d) a hindered phenol-based antioxidant, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the entire grease composition. . When the amount of (d) exceeds 10% by mass, the oxidation deterioration prevention is saturated, and when the amount of (d) is less than 0.1% by mass, the effect of addition cannot be obtained.

(e)金属不活性化剤としては、シュウ酸誘導体,サリチル酸誘導体,ヒドラジン誘導体などが挙げられ、具体的には、式(2)で表される3‐(N‐サリチロイル)アミノ‐1,2,4‐トリアゾール、式(3)で表されるデカメチレンカルボン酸ジサリチロイルヒドラジド(MCSH)、式(4)で表されるN,N‐ビス[3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオニル]ヒドラジン、イソフタル酸ビス(2‐フェノキシプロピオニルヒドラジド)、N‐ホルミル‐N'‐サリシロイルヒドラジン、2,2‐オキザミドビス‐[エチル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ハイドロオキシフェニル)プロピオネート]、オギザリル−ビス−ベンジリデン−ヒドラジドなどが挙げられる。このうち、式(3)で表されるデカメチレンカルボン酸ジサリチロイルヒドラジド(MCSH)が好ましい。   (E) Examples of the metal deactivator include oxalic acid derivatives, salicylic acid derivatives, hydrazine derivatives, and the like. Specifically, 3- (N-salicyloyl) amino-1,2 represented by the formula (2) , 4-triazole, decamethylenecarboxylic acid disalicyloyl hydrazide (MCSH) represented by formula (3), N, N-bis [3- (3,5-di-t represented by formula (4) -Butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, N-formyl-N'-salicyloylhydrazine, 2,2-oxamide bis- [ethyl-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], oxalyl-bis-benzylidene-hydrazide and the like. Of these, decamethylene carboxylic acid disalicyloyl hydrazide (MCSH) represented by the formula (3) is preferable.

3‐(N‐サリチロイル)アミノ‐1,2,4‐トリアゾール 3- (N-salicyloyl) amino-1,2,4-triazole

Figure 2013147548
Figure 2013147548

MCSH:デカメチレンカルボン酸ジサリチロイルヒドラジド MCSH: Decamethylene carboxylic acid disalicyloyl hydrazide

Figure 2013147548
Figure 2013147548

N,N‐ビス[3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオニル]ヒドラジン N, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine

Figure 2013147548
Figure 2013147548

本発明のグリース組成物は、グリース組成物全体に対して、(e)金属不活性化剤を、好ましくは0.1〜10質量%、より好ましくは0.1〜5質量%を含有する。(e)の量が10質量%を超えると、金属不活性化の効果が飽和し、(e)の量が0.1質量%未満であると、添加の効果が得られない。   The grease composition of the present invention contains (e) a metal deactivator, preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the entire grease composition. When the amount of (e) exceeds 10% by mass, the effect of metal deactivation is saturated, and when the amount of (e) is less than 0.1% by mass, the effect of addition cannot be obtained.

その他必要に応じて全ての添加剤が使用可能である。具体的には、本発明の必須成分である酸化防止剤以外の酸化防止剤、例えば、キノリン系酸化防止剤、アミン系酸化防止剤;錆止め剤;金属腐食防止剤;油性剤;耐摩耗剤;極圧剤;及び固体潤滑剤などがあげられる。   All other additives can be used as necessary. Specifically, antioxidants other than the antioxidant that is an essential component of the present invention, such as quinoline antioxidants, amine antioxidants; rust inhibitors; metal corrosion inhibitors; oil agents; antiwear agents; Extreme pressure agents; and solid lubricants.

本発明のグリース組成物は、グリース組成物全体に対して、(a)基油50質量%以上、好ましくは60質量%以上、(b)増ちょう剤1〜30質量%、好ましくは5〜20質量%、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物0.1〜10質量%、好ましくは0.5〜5質量%、(d)ヒンダードフェノール系酸化防止剤0.1〜10質量%、好ましくは0.5〜5質量%、(e)金属不活性化剤0.1〜10質量%、好ましくは0.1〜5質量%を含有するのが特に好ましい。   The grease composition of the present invention comprises (a) a base oil of 50% by mass or more, preferably 60% by mass or more, and (b) a thickener 1-30% by mass, preferably 5-20%, based on the entire grease composition. (C) 0.1 to 10% by mass of a compound having an alkylthiocarbamoyl group represented by the formula (1), preferably 0.5 to 5% by mass, (d) a hindered phenol antioxidant. 1 to 10% by weight, preferably 0.5 to 5% by weight, (e) 0.1 to 10% by weight, preferably 0.1 to 5% by weight, of a metal deactivator is particularly preferred.

〔混和ちょう度〕
本発明のグリース組成物の混和ちょう度は、好ましくは200〜400、より好ましくは250〜350である。混和ちょう度が400を上回ると、漏洩しやすい。一方、混和ちょう度が200を下回ると、撹拌抵抗が大きくなる。
[Mixing consistency]
The penetration of the grease composition of the present invention is preferably 200 to 400, more preferably 250 to 350. Leakage tends to occur when the penetration level exceeds 400. On the other hand, when the penetration is less than 200, the stirring resistance increases.

本発明のグリース組成物を封入する軸受としては、転がり軸受、特にころ軸受、なかでも円筒ころ軸受が好適である。全閉型のモータに使用される軸受、特に全閉型の鉄道車両用主電動機に使用される軸受が好ましい。軸受の材質は特に制限されないが、銅であるのが好ましい。   As the bearing for enclosing the grease composition of the present invention, a rolling bearing, particularly a roller bearing, particularly a cylindrical roller bearing is suitable. A bearing used for a fully-closed motor, particularly a bearing used for a fully-closed railway vehicle main motor is preferable. The material of the bearing is not particularly limited, but is preferably copper.

1.試験用グリース
表1及び表2に示した配合処方により、実施例1〜7、比較例1〜6のグリース組成物を調製した。各成分の量は、グリース組成物の全質量を基準とした質量%である。
1. Grease for Test Grease compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were prepared according to the formulation shown in Tables 1 and 2. The amount of each component is mass% based on the total mass of the grease composition.

2.グリースの製造方法
基油467.5gの中に12−ヒドロキシステアリン酸82.5gを加え、完全に透明な液体状態になる温度(80〜90℃)に加熱した。これに予め水60gに水酸化リチウム1水塩11.9gを添加して加熱溶解したものを加え、激しく攪拌しながら12−ヒドロキシステアリン酸のけん化反応を行って12−ヒドロキシステアリン酸のリチウム塩を形成した。次に、アゼライン酸26gを加えて均一な状態になるまで攪拌を継続した。これに予め水60gに水酸化リチウム1水塩11.9gを添加して加熱溶解したものを加え、激しく攪拌しながらアゼライン酸のけん化反応を行った。約60分後赤外分光分析で未反応脂肪酸の吸収が見られないことを確認してけん化反応を終了させた。次に、加熱工程に入り内容物を200℃まで徐々に加熱した。200℃になった時点で残りの基油400.2gを添加しそのまま室温まで冷却し、三段ロールを2回通して、リチウムコンプレックスグリースを得た。最終の内容物の量は1000gとした。
基油としては、エーテル油(アルキルジフェニルエーテル:動粘度 40℃ 100mm2/s, 100℃ 12.5mm2/s)と、エステル油(ペンタエリスリトールエステル:動粘度 40℃ 102mm2/s, 100℃ 12.9mm2/s)との1:1混合物(質量比)を使用した(動粘度 40℃ 101mm2/s)。
2. Method for producing grease 82.5 g of 12-hydroxystearic acid was added to 467.5 g of base oil and heated to a temperature (80 to 90 ° C.) at which a completely transparent liquid state was obtained. To this, 11.9 g of lithium hydroxide monohydrate was added to 60 g of water in advance and dissolved by heating, and saponification reaction of 12-hydroxystearic acid was performed with vigorous stirring to obtain a lithium salt of 12-hydroxystearic acid. Formed. Next, 26 g of azelaic acid was added and stirring was continued until a uniform state was achieved. A solution prepared by adding 11.9 g of lithium hydroxide monohydrate to 60 g of water and dissolving it by heating was added thereto, and saponification reaction of azelaic acid was performed with vigorous stirring. About 60 minutes later, it was confirmed by infrared spectroscopy that no unreacted fatty acid was observed, and the saponification reaction was terminated. Next, the heating process was started and the contents were gradually heated to 200 ° C. When the temperature reached 200 ° C., the remaining base oil (400.2 g) was added and cooled to room temperature as it was, and a three-stage roll was passed twice to obtain a lithium complex grease. The final content was 1000 g.
Base oils include ether oil (alkyl diphenyl ether: kinematic viscosity 40 ° C 100mm 2 / s, 100 ° C 12.5mm 2 / s) and ester oil (pentaerythritol ester: kinematic viscosity 40 ° C 102mm 2 / s, 100 ° C 12.9mm 2 / s) and a 1: 1 mixture (mass ratio) was used (kinematic viscosity 40 ° C. 101 mm 2 / s).

3.分析方法及び評価試験方法
(1)ちょう度 (JIS K2220 7)
ちょう度は、280に統一した。
(2)高温薄膜試験
60×80×1mmのSPCC鋼板にグリースを厚さ2mmで塗布し、試験前後の全酸価を測定した。試験後の全酸価は、規定温度(160℃)、規定時間(500h)後に測定した。全酸価は、JIS K2501 5.により測定した。
(3)軸受潤滑寿命試験
試験グリース(5.6g)を充填した軸受を試験機にセットした。軸受に対しラジアル荷重(100kgf)を負荷し、ヒータで軸受外輪温度を120℃一定に制御し、8000rpmの速度で回転させた。軸受外輪温度が130℃に達した時間を寿命時間とした。
[試験条件]
軸受 :円筒ころ軸受(型番:NU214、内径70mm、外径125mm)
荷重 :ラジアル荷重:100kgf
回転数 :8000rpm
グリース封入量:5.6g
温度 :120℃コントロール
3. Analysis method and evaluation test method (1) Consistency (JIS K2220 7)
The consistency was 280.
(2) High temperature thin film test
Grease was applied to a 60 × 80 × 1 mm SPCC steel plate with a thickness of 2 mm, and the total acid value before and after the test was measured. The total acid value after the test was measured after a specified temperature (160 ° C.) and a specified time (500 h). The total acid value was measured according to JIS K2501 5.
(3) Bearing lubrication life test A bearing filled with test grease (5.6 g) was set in a testing machine. A radial load (100 kgf) was applied to the bearing, the bearing outer ring temperature was controlled at a constant 120 ° C. with a heater, and the bearing was rotated at a speed of 8000 rpm. The time when the bearing outer ring temperature reached 130 ° C. was defined as the life time.
[Test conditions]
Bearing: Cylindrical roller bearing (model number: NU214, inner diameter 70 mm, outer diameter 125 mm)
Load: Radial load: 100kgf
Rotation speed: 8000rpm
Grease filling amount: 5.6 g
Temperature: 120 ° C control

評価基準
全酸価の変化(mgKOH/g) ○:0.20以下、×:0.20超
軸受潤滑寿命 ○:合格1000h超、×:不合格1000以下
総合評価 ○:全酸価変化及び軸受潤滑寿命の両方が合格
×:全酸価変化又は/及び軸受潤滑寿命が不合格
4.評価試験の結果
表1及び表2に実施例1〜7、比較例1〜6のグリース組成物の試験結果を示す。
Evaluation criteria Change in total acid value (mgKOH / g) ○: 0.20 or less, ×: More than 0.20 Bearing lubrication life ○: Passed over 1000h, ×: Fail 1000 or less Comprehensive evaluation ○: Both total acid value change and bearing lubrication life Passed
X: Total acid value change or / and bearing lubrication life failed. Results of Evaluation Test Tables 1 and 2 show the test results of the grease compositions of Examples 1 to 7 and Comparative Examples 1 to 6.

Figure 2013147548
Figure 2013147548

Figure 2013147548
Figure 2013147548

成分(a)〜(e)を含有する実施例1〜7は全酸価の変化が少なく熱酸化安定性に優れ、軸受潤滑寿命も全て基準を達成し、総合評価において合格であった。
一方、実施例1の(d)、(c)、(e)をそれぞれ含有しない比較例1、2、3は、全酸価の変化が大きく、熱酸化安定性に劣り、軸受潤滑寿命も短かかった。
また、実施例1の(d)の代わりに、キノリン系酸化防止剤、アミン系酸化防止剤をそれぞれ含有させた比較例4、5も全酸価の変化が大きく、熱酸化安定性に劣り、軸受潤滑寿命も短かかった。
実施例1の(d)の代わりに、キノリン系酸化防止剤とアミン系酸化防止剤とを含有させた比較例6についても同様に全酸価の変化が大きく、熱酸化安定性に劣り、軸受潤滑寿命も短かかった。
Examples 1 to 7 containing the components (a) to (e) were excellent in thermal oxidation stability with little change in the total acid value, all achieved the bearing lubrication life, and passed in the overall evaluation.
On the other hand, Comparative Examples 1, 2, and 3 that do not contain (d), (c), and (e) of Example 1 have a large change in total acid value, inferior thermal oxidation stability, and a short bearing lubrication life. It took.
Further, instead of Example 1 (d), Comparative Examples 4 and 5 containing a quinoline antioxidant and an amine antioxidant, respectively, have a large change in total acid value, and are inferior in thermal oxidation stability. The bearing lubrication life was also short.
In Comparative Example 6 containing a quinoline-based antioxidant and an amine-based antioxidant instead of (d) in Example 1, the change in the total acid value is similarly large, and the thermal oxidation stability is inferior. The lubrication life was also short.

Claims (7)

(a)基油、(b)増ちょう剤、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物、(d)ヒンダードフェノール系酸化防止剤、及び(e)金属不活性化剤を含有することを特徴とするグリース組成物。
(1)
Figure 2013147548

(式中、R1、R2、R3、R4は独立して炭素数1〜20のアルキル基を示し、Xは、S、S−S、S−CH2−S、S−CH2CH2−S又はS−CH2CH2CH2−Sを示す。)
(A) base oil, (b) thickener, (c) compound having alkylthiocarbamoyl group represented by formula (1), (d) hindered phenol antioxidant, and (e) metal deactivation A grease composition comprising an agent.
(1)
Figure 2013147548

(In the formula, R 1 , R 2 , R 3 and R 4 independently represent an alkyl group having 1 to 20 carbon atoms, and X represents S, S—S, S—CH 2 —S, S—CH 2. It shows a CH 2 -S or S-CH 2 CH 2 CH 2 -S.)
(d)ヒンダードフェノール系酸化防止剤が、2, 6-ジ-tert-ブチル-4-メチルフェノールである請求項1記載のグリース組成物。   (D) The grease composition according to claim 1, wherein the hindered phenol antioxidant is 2,6-di-tert-butyl-4-methylphenol. (e)金属不活性化剤が、デカメチレンカルボン酸ジサリチロイルヒドラジドである請求項1又は2記載のグリース組成物。   The grease composition according to claim 1 or 2, wherein (e) the metal deactivator is decamethylene carboxylic acid disalicyloyl hydrazide. (a)基油が、ポリオールエステル油とアルキルジフェニルエーテル油との混合油である請求項1〜3のいずれか1項記載のグリース組成物。   The grease composition according to any one of claims 1 to 3, wherein (a) the base oil is a mixed oil of a polyol ester oil and an alkyl diphenyl ether oil. (b)増ちょう剤が、リチウム石けん及び複合リチウム石けんからなる群から選ばれる少なくとも1種である請求項1〜4のいずれか1項記載のグリース組成物。   (B) The grease composition according to any one of claims 1 to 4, wherein the thickener is at least one selected from the group consisting of lithium soap and composite lithium soap. グリース組成物全体に対して、(a)基油50質量%以上、(b)増ちょう剤1〜30質量%、(c)式(1)で表されるアルキルチオカルバモイル基を有する化合物0.1〜10質量%、(d)ヒンダードフェノール系酸化防止剤0.1〜10質量%、(e)金属不活性0.1〜10質量%を含有する請求項1〜5のいずれか1項記載のグリース組成物。   (A) 50% by mass or more of base oil, (b) 1 to 30% by mass of thickener, (c) Compound 0.1 having an alkylthiocarbamoyl group represented by formula (1) with respect to the entire grease composition 10 mass%, (d) 0.1-10 mass% of hindered phenolic antioxidant, (e) metal inertness 0.1-10 mass% is contained, The any one of Claims 1-5 containing. Grease composition. 請求項1〜6のいずれか1項記載のグリース組成物を封入した軸受。   The bearing which enclosed the grease composition of any one of Claims 1-6.
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