JPWO2009153938A1 - Lubricant composition and lubrication system using the same - Google Patents

Lubricant composition and lubrication system using the same Download PDF

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JPWO2009153938A1
JPWO2009153938A1 JP2010517698A JP2010517698A JPWO2009153938A1 JP WO2009153938 A1 JPWO2009153938 A1 JP WO2009153938A1 JP 2010517698 A JP2010517698 A JP 2010517698A JP 2010517698 A JP2010517698 A JP 2010517698A JP WO2009153938 A1 JPWO2009153938 A1 JP WO2009153938A1
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lubricant composition
oil
lubricant
base oil
amide
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JP5383678B2 (en
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一泉 酒井
一泉 酒井
一聡 高橋
一聡 高橋
設楽 裕治
裕治 設楽
開米 貴
貴 開米
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Eneos Corp
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JX Nippon Oil and Energy Corp
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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
    • 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
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/065Sulfides; Selenides; Tellurides
    • C10M2201/066Molybdenum sulfide
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
    • 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
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/041Triaryl phosphates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/06Instruments or other precision apparatus, e.g. damping fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

【課題】小型化、高速化、高荷重化によってよりシビアとなっている摺動部材における諸問題を解決するため、摩擦、摩耗を大幅に低減し、かつ高い極圧性が示す潤滑剤組成物を提供する。【解決手段】鉱油系、合成油系及び/又は動植物油系の潤滑油基油に、アミド化合物を1〜70質量%、及びトリアジン誘導体を0.1〜50質量%含有する常温でゲル状の潤滑剤組成物及び該潤滑剤組成物を用いた潤滑システム。【選択図】なし[PROBLEMS] To provide a lubricant composition that greatly reduces friction and wear and exhibits high extreme pressure in order to solve various problems in sliding members that have become more severe due to downsizing, higher speed, and higher load. provide. [MEANS FOR SOLVING PROBLEMS] A lubricating base oil of mineral oil type, synthetic oil type and / or animal and vegetable oil type contains 1 to 70% by mass of an amide compound and 0.1 to 50% by mass of a triazine derivative at room temperature. Lubricant composition and lubrication system using the lubricant composition. [Selection figure] None

Description

本発明は、潤滑油基油に、アミド化合物とトリアジン誘導体を含有する常温でゲル状の潤滑剤組成物に関し、特にはトリアジン誘導体としてメラミンシアヌレート(MCA)を含有し、摺動部における摩耗を大幅に低減し、極圧性を大幅に向上して潤滑不良を改善し、潤滑システムの信頼性を向上した潤滑剤組成物に関する。また、本発明は該潤滑剤組成物を用いた潤滑システムに関する。   The present invention relates to a lubricant composition in a lubricating base oil containing an amide compound and a triazine derivative at room temperature, and in particular, contains melamine cyanurate (MCA) as a triazine derivative to reduce wear on a sliding portion. The present invention relates to a lubricant composition that greatly reduces, improves extreme pressure, improves poor lubrication, and improves the reliability of the lubrication system. The present invention also relates to a lubrication system using the lubricant composition.

精密機械、産業機械、輸送機械、測定機器などの機械システムには、各種軸受、歯車、ピストンシリンダー、駆動系などの様々な摺動部があり、絶えず摩擦摩耗を繰り返している。これらの摺動部において潤滑不良が生ずれば、潤滑システム、あるいはそれを含む機械システムは所望の働きができなくなってしまう。そのため、摺動部には各種の潤滑剤がその使用環境・条件に応じて用いられている。一般的には、潤滑油やグリースなどが広く用いられているが、摺動部を構成する部材自体に優れた潤滑性を有する材料が使用されていたり、もしくは優れた潤滑性を付与する表面処理を行うなど様々な対応が施されている。   There are various sliding parts such as various bearings, gears, piston cylinders, and drive systems in mechanical systems such as precision machines, industrial machines, transportation machines, and measuring instruments, and frictional wear is constantly repeated. If poor lubrication occurs in these sliding parts, the lubrication system or a mechanical system including the lubrication system cannot perform a desired function. Therefore, various lubricants are used for the sliding portion according to the use environment and conditions. In general, lubricating oils and greases are widely used, but materials that have excellent lubricity are used for the members constituting the sliding parts themselves, or surface treatment that imparts excellent lubricity Various measures such as doing are given.

潤滑剤として一般に使用されている液状の潤滑油、半固体状のグリースなどのなかで、特にリチウム(Li)石けんやカルシウム(Ca)石けん、あるいはウレアを増ちょう剤として配合したグリースでは固体潤滑剤を混合して耐摩耗性を向上させているケースがあり、一定の効果をあげている。固体潤滑剤としては、二硫化モリブデン、グラファイト、ポリテトラフルオロエチレン(PTFE)、窒化ホウ素(BN)などが一般的に用いられている。
しかし、昨今、機械システムの小型、高速化、高荷重化により摺動部における負荷が高まり、より耐摩耗性や極圧性などの潤滑性に優れる潤滑剤が求められている。さらには、極少量での油量でも十分な潤滑性が確保できる潤滑剤が求められている。
Among the lubricating oils and semi-solid greases that are commonly used as lubricants, solid lubricants are especially used for greases that contain lithium (Li) soap, calcium (Ca) soap, or urea as a thickener. In some cases, the wear resistance is improved by mixing, which has a certain effect. As the solid lubricant, molybdenum disulfide, graphite, polytetrafluoroethylene (PTFE), boron nitride (BN) and the like are generally used.
However, in recent years, the load on the sliding portion has increased due to the reduction in size, speed, and load of the mechanical system, and a lubricant that is more excellent in lubricity such as wear resistance and extreme pressure has been demanded. Furthermore, there is a demand for a lubricant that can ensure sufficient lubricity even with an extremely small amount of oil.

一方、Liグリースやウレアグリースに比べ、低摩擦特性を有する熱可逆性ゲル状潤滑剤も開発されている(特許文献1)。しかし、極めて潤滑条件の厳しい用途では、より一層高い極圧性や耐摩耗性が求められている。   On the other hand, a thermoreversible gel-like lubricant having low friction characteristics compared to Li grease and urea grease has also been developed (Patent Document 1). However, in applications where the lubrication conditions are severe, higher extreme pressure properties and wear resistance are required.

国際公開番号WO2006/051671International Publication Number WO2006 / 051671

本発明は、高速化、高荷重化、少油量化によってより一層シビアとなっている摺動部材における諸問題を解決することを目的とする。すなわち、本発明は、極少量の油量でも十分な潤滑性を有し、特には摩擦、摩耗を低減し、かつ高い極圧性を有する潤滑剤組成物を提供することを課題とする。また本発明は、かかる潤滑剤組成物を用いた潤滑システムを提供することを課題とする。   An object of the present invention is to solve various problems in a sliding member that is more severe due to higher speed, higher load, and less oil. That is, an object of the present invention is to provide a lubricant composition that has sufficient lubricity even with an extremely small amount of oil, particularly reduces friction and wear, and has high extreme pressure properties. Another object of the present invention is to provide a lubrication system using such a lubricant composition.

本発明者は、潤滑剤の性能を向上させて前記の課題を解決するため、様々な材料、その形態や性状、及び各種材料の配合割合などについて調査、研究した結果、トリアジン誘導体、特にはメラミンシアヌレート(MCA)を、アミド化合物をゲル化剤として含有する熱可逆性ゲル状潤滑剤に配合することによりその潤滑性を大幅に向上できることを見出した。そして、かかる知見に基づいて本発明を完成した。   In order to solve the above-mentioned problems by improving the performance of the lubricant, the present inventors have investigated and studied various materials, their forms and properties, and the blending ratio of various materials. As a result, triazine derivatives, particularly melamine, have been studied. It has been found that the lubricity of cyanurate (MCA) can be greatly improved by blending cyanurate (MCA) with a thermoreversible gel lubricant containing an amide compound as a gelling agent. And based on this knowledge, this invention was completed.

すなわち、本発明は次のとおりの潤滑剤組成物及びこれを用いた潤滑システムである。
(1)鉱油系、合成油系及び/又は動植物油系の潤滑油基油に、アミド化合物を1〜70質量%、及びトリアジン誘導体を0.1〜50質量%含有する常温でゲル状の潤滑剤組成物。
That is, the present invention is the following lubricant composition and a lubrication system using the same.
(1) Lubricant in a gel form at normal temperature containing 1 to 70% by mass of an amide compound and 0.1 to 50% by mass of a triazine derivative in a mineral base oil, synthetic oil base and / or animal or vegetable base oil Agent composition.

(2)トリアジン誘導体がメラミンシアヌレート(MCA)である上記(1)に記載の潤滑剤組成物。
(3)潤滑油基油は40℃における動粘度が5〜1000mm/sである上記(1)又は(2)に記載の潤滑剤組成物。
(4)ちょう度が90〜400である上記(1)〜(3)のいずれかに記載の潤滑剤組成物。
(2) The lubricant composition according to the above (1), wherein the triazine derivative is melamine cyanurate (MCA).
(3) The lubricant composition according to (1) or (2), wherein the lubricant base oil has a kinematic viscosity at 40 ° C. of 5 to 1000 mm 2 / s.
(4) The lubricant composition according to any one of (1) to (3), wherein the consistency is 90 to 400.

(5)さらに、モリブデン化合物をモリブデン(Mo)として0.1〜10質量%含有する上記(1)〜(4)のいずれかに記載の潤滑剤組成物。 (5) The lubricant composition according to any one of (1) to (4), further containing 0.1 to 10% by mass of a molybdenum compound as molybdenum (Mo).

(6) 上記(1)〜(5)のいずれかに記載の潤滑剤組成物を用いることを特徴とする潤滑システム。 (6) A lubricating system using the lubricant composition according to any one of (1) to (5) above.

本発明の潤滑剤組成物は、作動時に低摩擦特性を有する常温でゲル状の熱可逆性潤滑剤に、極圧性が高く、微細で固体潤滑剤として作用するMCAを含有するので、摩耗が顕著に低減され、かつ摩擦係数も低く安定する特性を有する。したがって、本発明の潤滑剤組成物は、潤滑条件の厳しい機械システムの長寿命化に貢献し、かつ低く安定した摩擦係数の特性から省エネルギーにも寄与するなど格別な効果を奏する。   Since the lubricant composition of the present invention contains MCA that acts as a fine and solid lubricant in a gel-like thermoreversible lubricant that has a low friction characteristic at the time of operation and has a high extreme pressure, wear is remarkable. And has a characteristic that the friction coefficient is low and stable. Therefore, the lubricant composition of the present invention contributes to extending the life of a mechanical system having severe lubrication conditions, and has a special effect such as contributing to energy saving due to a low and stable characteristic of a friction coefficient.

本発明の潤滑剤組成物は、鉱油系、合成油系及び/又は動植物油系の潤滑油基油とアミド化合物を含有する常温でゲル状の熱可逆性潤滑剤において、トリアジン誘導体、特にはMCAを0.1〜50質量%含有することを特徴とする。   The lubricant composition of the present invention is a gel-like thermoreversible lubricant containing a mineral oil-based, synthetic oil-based and / or animal and vegetable oil-based lubricant base oil and an amide compound. Is contained in an amount of 0.1 to 50% by mass.

〔潤滑剤組成物〕
本発明の常温でゲル状の熱可逆性を有する潤滑剤組成物は、潤滑油基油に、ゲル化剤としてアミド化合物を、さらに摩擦、摩耗を低減する効果を有する成分としてトリアジン誘導体を含有する組成物である。グリースと比較した常温でゲル状の潤滑剤組成物の特長としては、摺動部分が作動時には摩擦熱によって液体状となって摺動部に浸入して潤滑油膜を形成し、停止時には摺動部の温度が低下して常温になり、潤滑剤組成物は半固体状になる。したがって、作動時にはゲル化剤自体が油性剤であり摩擦係数を大幅に下げ、また付着力が強く薄膜状態でも油膜を長時間維持できることなどの利点が挙げられる。また低温でのトルクが小さく、停止時や摺動部から離れた位置における低温状態ではゲル状となって蒸発性を低く抑えられるなどの利点もある。用途はグリースが使われている分野により好ましく用いることができるが、グリースでは特性が充分でない特殊な機器、部分、条件下でも使うことができる。
[Lubricant composition]
The lubricant composition having a gel-like thermoreversibility according to the present invention contains an amide compound as a gelling agent and a triazine derivative as a component having an effect of reducing friction and wear in a lubricating base oil. It is a composition. The characteristic of a lubricant composition that is gel at room temperature compared to grease is that the sliding part becomes liquid by frictional heat when operating and enters the sliding part to form a lubricating oil film, and when the sliding part stops, the sliding part The temperature of the lubricant decreases to normal temperature, and the lubricant composition becomes semi-solid. Accordingly, there are advantages such that the gelling agent itself is an oily agent during operation and the friction coefficient is greatly reduced, and that the oil film can be maintained for a long time even in a thin film state with strong adhesion. In addition, the torque at a low temperature is small, and there is an advantage that the evaporability can be kept low by becoming a gel when stopped or at a low temperature in a position away from the sliding portion. Applications can be preferably used depending on the field in which the grease is used, but it can also be used in special equipment, parts, and conditions where the properties of the grease are not sufficient.

本発明の潤滑剤組成物は、90〜400のちょう度を有するものが、潤滑システムでの適用粘性や機器等への充填時等で取扱いが容易であるので、好ましい。
なお、ここで「常温」とは室内の普通の温度を意味し、具体的には、50℃以下、より一般的には−10〜30℃程度の温度環境をいう。
The lubricant composition of the present invention having a consistency of 90 to 400 is preferable because it is easy to handle due to application viscosity in a lubrication system or filling into equipment.
Here, “normal temperature” means an ordinary temperature in the room, specifically, a temperature environment of 50 ° C. or less, more generally about −10 to 30 ° C.

〔潤滑油基油〕
本発明において、潤滑油基油としては、鉱油系、合成油系、動植物油系などの潤滑油基油を用いることができる。さらに、これらの潤滑油基油を2種以上混合して用いてもかまわない。
潤滑油基油の物性としては、特に限定するものではないが、軸受や歯車などの潤滑システムで適用されうる適正粘性,油膜形成能のため、40℃における動粘度が5〜1000mm/sのものが好ましく、10〜600mm/sのものがより好ましく、さらに好ましくは20〜500mm/sである。また、幅広い温度域で安定した潤滑性能維持のため、粘度指数は90以上が好ましく、より好ましくは100〜250であり、低温作動性のため、流動点は−10℃以下が好ましく、より好ましくは−15〜−70℃であり、また、潤滑システムおよび取扱い上の安全のため、引火点は150℃以上が好ましく、より好ましくは200℃以上である。
[Lubricant base oil]
In the present invention, as the lubricating base oil, a lubricating base oil such as mineral oil, synthetic oil, animal or vegetable oil can be used. Further, two or more of these lubricating base oils may be used in combination.
The physical properties of the lubricating base oil are not particularly limited, but the kinematic viscosity at 40 ° C. is 5 to 1000 mm 2 / s because of appropriate viscosity and oil film forming ability that can be applied in lubrication systems such as bearings and gears. A thing of 10-600 mm < 2 > / s is more preferable, More preferably, it is 20-500 mm < 2 > / s. In order to maintain stable lubricating performance in a wide temperature range, the viscosity index is preferably 90 or more, more preferably 100 to 250, and for low temperature operability, the pour point is preferably −10 ° C. or less, more preferably. The flash point is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, for the safety of the lubrication system and handling.

鉱油系の潤滑油基油としては、原油を常圧蒸留して、さらには減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱蝋、水素化脱蝋、水素化精製、硫酸洗浄、白土処理等の潤滑油精製手段を適宜組み合わせて処理して得られた精製潤滑油留分を好適に用いることができる。各種の原料と各種の精製手段の組み合わせから得られた性状の異なる精製潤滑油留分を単独で用いてもよいし、2種以上を組み合わせて用いることもできる。このように石油の比較的高沸点な留分より作られる鉱油系の潤滑油基油は一般的に安価なこともあり、様々な潤滑油やグリースなどに広く用いられている。   As a mineral oil base oil, the crude oil fraction obtained by atmospheric distillation and then vacuum distillation is used to remove solvent oil, solvent extraction, hydrocracking, solvent dewaxing, hydrogenation. A refined lubricating oil fraction obtained by treating lubricating oil refining means such as dewaxing, hydrorefining, sulfuric acid washing, and clay treatment as appropriate can be suitably used. Refined lubricating oil fractions having different properties obtained from a combination of various raw materials and various purification means may be used alone or in combination of two or more. Mineral oil base oils made from a fraction having a relatively high boiling point of petroleum are generally inexpensive and are widely used for various lubricating oils and greases.

また、合成油系の潤滑油基油としては、ポリ‐α‐オレフィン(PAO)、エチレン‐α‐オレフィンオリゴマーなどのポリ‐α‐オレフィンオリゴマー、アルキルベンゼン、アルキルナフテン、アルキルナフタレン、グリコール、エステル、エーテル、シリコーン油、フッ素化油などが挙げられる。なかでもPAO、エステルが、特にPAOが、粘度特性、酸化安定性、材料適合性、コストの面で優れており、好ましく用いることができる。これらの合成油は、上記の物性を満足するのであれば、単独で用いることもできるし、2種以上を組み合わせて用いることもできる。   Synthetic oil base oils include poly-α-olefin (PAO), poly-α-olefin oligomers such as ethylene-α-olefin oligomers, alkylbenzenes, alkylnaphthenes, alkylnaphthalenes, glycols, esters, ethers. , Silicone oil, fluorinated oil, and the like. Of these, PAO and esters, especially PAO, are excellent in terms of viscosity characteristics, oxidation stability, material compatibility, and cost, and can be preferably used. These synthetic oils can be used alone or in combination of two or more as long as the above physical properties are satisfied.

ポリ‐α‐オレフィンは、化学的に不活性であり、粘度特性に優れ、幅広い粘度を有するものが市販されておりコスト面でも好ましい。ポリ‐α‐オレフィンは、1‐デセンや1‐ドデセン、あるいは1‐テトラデセンなどのオレフィンオリゴマーを重合し、重合度2〜10の範囲で、これら重合物を粘度調整のために適宜配合したものを好ましく使用することができる。   Poly-α-olefins are chemically inert, have excellent viscosity characteristics, and have a wide range of viscosities, which are preferred in terms of cost. Poly-α-olefin is obtained by polymerizing olefin oligomers such as 1-decene, 1-dodecene, or 1-tetradecene, and blending these polymers appropriately for viscosity adjustment within the range of polymerization degree 2-10. It can be preferably used.

エステルも様々な分子構造の化合物が市販されており、それぞれ特有の粘度特性(高粘度指数、低流動点)を有し、同一粘度である炭化水素系基油と比べると引火点が高い特徴がある基油である。エステルは、アルコールと脂肪酸を脱水縮合反応して得ることができるが、本発明においては、化学的な安定性の面で、二塩基酸と1価アルコールとのジエステル、ポリオール(特にはネオペンチルポリオール)と1価脂肪酸とのポリオールエステル、またはポリオールと多価塩基酸と1価アルコール(又は1価脂肪酸)とのコンプレックスエステルを好適な基油成分として挙げることができる。   Esters are also commercially available as compounds with various molecular structures, each having unique viscosity characteristics (high viscosity index, low pour point), and high flash point compared to hydrocarbon base oils of the same viscosity. A base oil. Esters can be obtained by dehydration condensation reaction of alcohols and fatty acids. In the present invention, however, diesters and polyols (particularly neopentyl polyols) of dibasic acids and monohydric alcohols in terms of chemical stability. ) And a monovalent fatty acid, or a complex ester of a polyol, a polybasic acid and a monohydric alcohol (or monohydric fatty acid) can be mentioned as a suitable base oil component.

動植物油系の潤滑油基油としては、菜種油、大豆油などが挙げられる。
通常、これら鉱油系、合成油系、動植物油系などの潤滑油基油は適宜組み合わせ、用途ごとに要求される様々な性能を満たすように適宜の割合で配合することができる。このとき、鉱油系、合成油系及び動植物油系の潤滑油基油はそれぞれ複数用いてもかまわない。
Examples of animal and vegetable oil-based lubricating base oils include rapeseed oil and soybean oil.
Usually, these base oils such as mineral oils, synthetic oils and animal and vegetable oils can be appropriately combined and blended at an appropriate ratio so as to satisfy various performances required for each application. At this time, a plurality of mineral oil-based, synthetic oil-based and animal and vegetable oil-based lubricating base oils may be used.

〔アミド化合物〕
本発明において、アミド化合物は前記の潤滑油基油と混合して常温でゲル状の潤滑剤組成物を調製するために用いる。アミド化合物は、グリースの増ちょう剤に相当するゲル化剤として作用し、本発明の潤滑剤組成物に、ゲル化剤の融点を超えると液体になり、融点以下だと半固体状(ゲル状)となる熱可逆性の温度特性を付与する。
[Amide compound]
In the present invention, the amide compound is mixed with the above lubricating base oil and used to prepare a gel-like lubricant composition at room temperature. The amide compound acts as a gelling agent corresponding to a thickener of grease. In the lubricant composition of the present invention, the amide compound becomes liquid when the melting point of the gelling agent is exceeded, and is semi-solid (gelled) below the melting point. ) To give thermoreversible temperature characteristics.

本発明に用いるアミド化合物は、アミド基(‐NH‐CO‐)を1つ以上有する脂肪酸アミド化合物で、次の式(1)で表されるアミド基が1個のモノアミド、及び式(2)及び(3)で表されるアミド基を2個有するビスアミドを好ましく用いることができる。

Figure 2009153938
式中、R及びRは、それぞれ独立して、炭素数5〜25の飽和又は不飽和の鎖状炭化水素基であり、さらに、Rは水素であってもよい。
Figure 2009153938
Figure 2009153938
式(2)及び(3)において、R、R、R及びRは、それぞれ独立して、炭素数5〜25の飽和又は不飽和の鎖状炭化水素基であり、A及びAは、炭素数1〜10のアルキレン基、フェニレン基又は炭素数7〜10のアルキルフェニレン基から選択される炭素数1〜10の2価の炭化水素基である。なお、アルキルフェニレン基の場合、フェニレン基とアルキル基及び/又はアルキレン基の2個以上とが結合したかたちの2価の炭化水素基であってもよい。The amide compound used in the present invention is a fatty acid amide compound having one or more amide groups (—NH—CO—), a monoamide having one amide group represented by the following formula (1), and the formula (2) And a bisamide having two amide groups represented by (3) can be preferably used.
Figure 2009153938
In the formula, R 1 and R 2 are each independently a saturated or unsaturated chain hydrocarbon group having 5 to 25 carbon atoms, and R 2 may be hydrogen.
Figure 2009153938
Figure 2009153938
In the formulas (2) and (3), R 3 , R 4 , R 5 and R 6 are each independently a saturated or unsaturated chain hydrocarbon group having 5 to 25 carbon atoms, and A 1 and a 2 is a divalent hydrocarbon group having 1 to 10 carbon atoms selected from an alkylene group, an alkyl phenylene group having a phenylene group or a 7 to 10 carbon atoms having 1 to 10 carbon atoms. In the case of an alkylphenylene group, it may be a divalent hydrocarbon group in which two or more of a phenylene group and an alkyl group and / or an alkylene group are bonded.

モノアミド化合物は、上記式(1)で表されるが、R及びRを構成する水素の一部は水酸基で置換されていてもよい。このようなモノアミド化合物として、具体的には、ラウリン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘン酸アミド、ヒドロキシステアリン酸アミド等の飽和脂肪酸アミド、オレイン酸アミド、エルカ酸アミドなどの不飽和脂肪酸アミド、及びステアリルステアリン酸アミド、オレイルオレイン酸アミド、オレイルステアリン酸アミド、ステアリルオレイン酸アミド等の飽和又は不飽和の長鎖脂肪酸と長鎖アミンによる置換アミド類などが挙げられる。
これらのモノアミド化合物の中でも、式(1)のR及びRがそれぞれ独立して炭素数12〜20の飽和鎖状炭化水素基のアミド化合物及び/又はRとRの少なくともいずれか一方が炭素数12〜20の不飽和鎖状炭化水素基のアミド化合物であることが好ましく、両アミド化合物の混合物がより好ましい。さらに不飽和鎖状炭化水素基が炭素数18の不飽和結合を有するオレイル基であるモノアミド化合物が好ましい。具体的にはオレイン酸アミド、オレイルオレイン酸アミドが好ましく、摺動部に薄膜を形成し、保持し、焼付トラブルの解消に効果的な薄膜保持性を確保する。
The monoamide compound is represented by the above formula (1), but a part of hydrogen constituting R 1 and R 2 may be substituted with a hydroxyl group. Specific examples of such monoamide compounds include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide, and unsaturated fatty acids such as oleic acid amide and erucic acid amide. Examples thereof include amides, and substituted amides with saturated or unsaturated long-chain fatty acids and long-chain amines such as stearyl stearamide, oleyl oleate, oleyl stearate, stearyl oleamide, and the like.
Among these monoamide compounds, R 1 and R 2 in the formula (1) are each independently an amide compound having a saturated chain hydrocarbon group having 12 to 20 carbon atoms and / or at least one of R 1 and R 2. Is preferably an amide compound of an unsaturated chain hydrocarbon group having 12 to 20 carbon atoms, and more preferably a mixture of both amide compounds. Furthermore, a monoamide compound in which the unsaturated chain hydrocarbon group is an oleyl group having an unsaturated bond having 18 carbon atoms is preferred. Specifically, oleic acid amide and oleyl oleic acid amide are preferable, and a thin film is formed and held on the sliding portion, and the thin film retainability effective in solving the seizure trouble is ensured.

ビスアミド化合物としては、ジアミンの酸アミド又はジ酸の酸アミドの形をした上記式(2)又は(3)でそれぞれ表される化合物である。なお、式(2)及び(3)でR、R、R及びR、さらにA及びAで表される炭化水素基において、一部の水素が水酸基(‐OH)で置換されていてもよい。
式(2)で表されるアミド化合物として、具体的には、エチレンビスステアリン酸アミド、エチレンビスイソステアリン酸アミド、エチレンビスオレイン酸アミド、メチレンビスラウリン酸アミド、ヘキサメチレンビスオレイン酸アミド、ヘキサメチレンビスヒドロキシステアリン酸アミド、m−キシリレンビスステアリン酸アミド等が挙げられる。式(3)で表されるアミド化合物として、具体的には、N,N’‐ジステアリルセバシン酸アミド等が挙げられる。
The bisamide compound is a compound represented by the above formula (2) or (3) in the form of a diamine acid amide or a diacid acid amide. In addition, in the hydrocarbon groups represented by R 3 , R 4 , R 5 and R 6 , and A 1 and A 2 in the formulas (2) and (3), some hydrogens are substituted with hydroxyl groups (—OH). May be.
Specific examples of the amide compound represented by the formula (2) include ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bisoleic acid amide, methylene bislauric acid amide, hexamethylene bisoleic acid amide, hexamethylene Examples thereof include bishydroxystearic acid amide and m-xylylene bisstearic acid amide. Specific examples of the amide compound represented by the formula (3) include N, N′-distearyl sebacic acid amide.

これらビスアミド化合物の中でも、モノアミド化合物の場合と同様に、式(2)のRとR及び式(3)のRとRがそれぞれ独立して炭素数12〜20の飽和鎖状炭化水素基のアミド化合物及び/又はRとR及びRとRの少なくともいずれか一方が炭素数12〜20の不飽和鎖状炭化水素基のアミド化合物であることが好ましく、両アミド化合物の混合物がより好ましい。さらに不飽和鎖状炭化水素基が炭素数18の不飽和結合を有するオレイル基であるビスアミド化合物が薄膜保持性を確保する上で好ましい。このような化合物として、エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミドなどが挙げられる。Among these bisamide compounds, as in the case of the monoamide compound, R 3 and R 4 in the formula (2) and R 5 and R 6 in the formula (3) are each independently a saturated chain carbonization having 12 to 20 carbon atoms. Preferably, the amide compound of a hydrogen group and / or at least one of R 3 and R 4 and R 5 and R 6 is an amide compound of an unsaturated chain hydrocarbon group having 12 to 20 carbon atoms, both amide compounds The mixture of is more preferable. Further, a bisamide compound in which the unsaturated chain hydrocarbon group is an oleyl group having an unsaturated bond having 18 carbon atoms is preferable for ensuring thin film retention. Examples of such compounds include ethylene bisoleic acid amide and hexamethylene bisoleic acid amide.

また機械システムの設計上の制約から極少量の油剤しか用いることができない摺動部で厳しい潤滑環境下においても焼付きなどを起こさないためには、摺動表面に油剤が強固に吸着・付着し、油膜を保持しなければならない。そのためには付着性を有する油剤が必要であるが、本発明では、ゲル化剤であるアミド化合物の炭化水素基が不飽和鎖状であると付着性が増す。付着性が増すと摺動表面へ薄膜状に塗布することができ、厳しい潤滑環境においても油膜切れを起こしにくくなり、潤滑性能が向上する。不飽和鎖状炭化水素基としては、炭素数12〜20の不飽和結合を有するアルケニル基、特には炭素数18の不飽和結合を有するオレイル基であるビスアミド化合物が好ましい。   In order to prevent seizure in a severe lubrication environment at sliding parts where only a small amount of oil can be used due to mechanical system design restrictions, the oil adheres firmly to the sliding surface. Must hold the oil film. For this purpose, an oil agent having adhesiveness is required, but in the present invention, if the hydrocarbon group of the amide compound that is a gelling agent is an unsaturated chain, the adhesiveness is increased. When the adhesion increases, it can be applied to the sliding surface in a thin film, and it becomes difficult to cause an oil film breakage even in a severe lubrication environment, and the lubrication performance is improved. The unsaturated chain hydrocarbon group is preferably a bisamide compound which is an alkenyl group having an unsaturated bond having 12 to 20 carbon atoms, particularly an oleyl group having an unsaturated bond having 18 carbon atoms.

アミド化合物は、仕上がりの常温で半固体状である潤滑剤組成物に1〜70質量%含まれるように配合する。アミド化合物の配合量が、1質量%未満では、常温でゲル状の組成物を形成することができず、一方、90質量%を超えて配合しても硬くなりすぎてハンドリングしにくくなり、好ましくない。より好ましい配合量は1〜50質量%で、5〜30質量%が特に好ましい。   An amide compound is mix | blended so that it may be contained at 1-70 mass% in the lubricant composition which is semi-solid at the normal temperature of a finish. If the amount of the amide compound is less than 1% by mass, a gel-like composition cannot be formed at room temperature. On the other hand, if it exceeds 90% by mass, it becomes too hard and difficult to handle. Absent. A more preferable blending amount is 1 to 50% by mass, and 5 to 30% by mass is particularly preferable.

〔トリアジン誘導体〕
本発明で用いることのできるトリアジン誘導体としては、メラミン類やシアヌル酸類、またメラミン類とシアヌル酸類の付加物等が挙げられる。シアヌル酸類としては、シアヌル酸やイソシアヌル酸、トリメチルシアヌレート、トリエチルシアヌレート、メチルシアヌレート、ジエチルシアヌレート、トリノルマルプロピルシアヌレート、及びそれらの水和物でも無水物であってもよい。メラミン類としては、メラミン、アンメリド、アンメリン、ホルモグアナミン、グアニルメラミン、シアノメラミン、アリルグアナミン、リン酸メラミン等が挙げられる。メラミン類とシアヌル酸類との付加物としては、前記メラミン類とシアヌル酸類の付加物、好ましくは等モル付加物が挙げられ、付加物はメラミン類とシアヌル酸類の水溶液を混合して両者の塩を形成させ、濾過して得ることができる。
[Triazine derivative]
Examples of the triazine derivative that can be used in the present invention include melamines and cyanuric acids, and adducts of melamines and cyanuric acids. The cyanuric acids may be cyanuric acid, isocyanuric acid, trimethyl cyanurate, triethyl cyanurate, methyl cyanurate, diethyl cyanurate, trinormal propyl cyanurate, and their hydrates or anhydrides. Examples of melamines include melamine, ammelide, ammelin, formoguanamine, guanylmelamine, cyanomelamine, allylguanamine, and melamine phosphate. Examples of the adduct of melamines and cyanuric acids include the adducts of melamines and cyanuric acids, preferably equimolar adducts, which are mixed with an aqueous solution of melamines and cyanuric acids to form salts of both. Can be formed and filtered.

本発明の潤滑剤組成物において、トリアジン誘導体としては、特にはメラミンとイソシアヌル酸の付加物であるメラミンシアヌレート(MCA)などで、平均粒径が10μm以下の極めて微細な粉末状のものを用いることが好ましい。トリアジン誘導体をこのような微粉末で用いると、潤滑剤組成物中に均一に分散される。平均粒径が10μm以下といった極めて微細な粒子は、潤滑剤組成物に配合すると、沈降したり、粒子同士が凝集して不均一な濃度分布を形成したりすることがない。均一な濃度での分散状態を長期間に亘って保持することができる。   In the lubricant composition of the present invention, as the triazine derivative, melamine cyanurate (MCA), which is an adduct of melamine and isocyanuric acid, in particular, an extremely fine powder having an average particle size of 10 μm or less is used. It is preferable. When the triazine derivative is used in such a fine powder, it is uniformly dispersed in the lubricant composition. When extremely fine particles having an average particle size of 10 μm or less are blended in the lubricant composition, they do not settle or aggregate and form a non-uniform concentration distribution. A dispersed state at a uniform concentration can be maintained over a long period of time.

そして、微細なトリアジン誘導体を均一な分散状態で含有した潤滑剤組成物は、摺動面における摩擦、摩耗を顕著に低減する。この詳細なメカニズムは明確ではないが、トリアジン誘導体の微細粒子が摺動部において良好な固体潤滑剤として働き摺動抵抗を軽減することに加えて、さらにトリアジン誘導体の微細粒子がゲル化剤のアミド化合物と水素結合で結合して摺動面に複合被膜を形成し、これがさらに相乗的に摩擦を減じ、摩耗を抑制するものと推察される。さらにトリアジン誘導体とアミド系ゲル化剤の水素結合は、せん断安定性を高める作用があり、不混和ちょう度と混和ちょう度の変化を少なくする作用がある。10μm以上の大きな粒子では、摺動面に導入されにくくなるばかりでなく、潤滑剤組成物での安定な分散性が劣るなどの欠点が生じる。平均粒径は0.1〜5μmがより好ましく、0.1〜2μmが特に好ましい。なお、本発明において、平均粒径は、走査型電子顕微鏡より算術平均して求めた値である。
なお、トリアジン誘導体のなかでもMCAは、非ハロゲン系の難燃助剤として使われているように化学的に安定な微粉末であり、比較的安価に市販されている。したがって、入手しやすく、また粒径を10μm以下に選別し生産する技術も確立されている。
A lubricant composition containing a fine triazine derivative in a uniform dispersed state significantly reduces friction and wear on the sliding surface. Although the detailed mechanism is not clear, in addition to the fine particles of the triazine derivative acting as a good solid lubricant in the sliding portion to reduce the sliding resistance, the fine particles of the triazine derivative are further added to the amide of the gelling agent. It is presumed that the compound is bonded to the compound by hydrogen bonding to form a composite film on the sliding surface, which further reduces the friction and suppresses wear. Further, the hydrogen bond between the triazine derivative and the amide-based gelling agent has an effect of increasing the shear stability and has an effect of reducing the immiscibility and the change in the miscibility. Large particles of 10 μm or more are not only difficult to be introduced into the sliding surface, but also have disadvantages such as poor stable dispersibility in the lubricant composition. The average particle size is more preferably from 0.1 to 5 μm, particularly preferably from 0.1 to 2 μm. In the present invention, the average particle diameter is a value obtained by arithmetic averaging with a scanning electron microscope.
Of the triazine derivatives, MCA is a chemically stable fine powder used as a non-halogen flame retardant aid, and is commercially available at a relatively low cost. Therefore, it is easy to obtain and a technique for selecting and producing a particle size of 10 μm or less has been established.

トリアジン誘導体は、好ましくは潤滑剤組成物に0.1〜50質量%含有されるように配合する。より好ましくは1〜20重量%である。0.1質量%未満では、トリアジン誘導体の添加の効果が得られず、一方、50質量%を超える量配合しても増量に見合うトリアジン誘導体の添加の効果が得られない。   The triazine derivative is preferably blended so as to be contained in the lubricant composition in an amount of 0.1 to 50% by mass. More preferably, it is 1 to 20% by weight. If the amount is less than 0.1% by mass, the effect of adding a triazine derivative cannot be obtained. On the other hand, even if the amount exceeds 50% by mass, the effect of adding a triazine derivative commensurate with the increase cannot be obtained.

〔潤滑剤組成物の調製〕
本発明の潤滑剤組成物は、潤滑油基油とアミド化合物からなる常温でゲル状の混合物にトリアジン誘導体が均一に分散して含有されているのであれば、より好ましくは、平均粒径が10μm以下のMCAの微細粒子が均一に分散、含有されている状態で得られるのであれば、いかなる方法で調製してもかまわない。潤滑油基油とアミド化合物の半固体・ゲル状混合物に特殊なミキサーを用いて、常温で潤滑剤組成物を調製することは可能であるが、取り扱いが面倒であり、効率的でもない。したがって、潤滑油基油とアミド化合物の混合物を一旦液状ないし液体に近い状態に昇温してMCAなどのトリアジン誘導体をブレンドすると比較的容易に本発明の潤滑剤組成物を調製することができる。
(Preparation of lubricant composition)
The lubricant composition of the present invention is more preferably an average particle diameter of 10 μm as long as the triazine derivative is uniformly dispersed in a gel-like mixture composed of a lubricating base oil and an amide compound at room temperature. The following MCA fine particles may be prepared by any method as long as they are obtained in a state where they are uniformly dispersed and contained. Although it is possible to prepare a lubricant composition at a normal temperature using a special mixer for a semi-solid / gel mixture of a lubricating base oil and an amide compound, handling is troublesome and not efficient. Therefore, the lubricant composition of the present invention can be prepared relatively easily when the mixture of the lubricant base oil and the amide compound is once heated to a liquid or nearly liquid state and blended with a triazine derivative such as MCA.

したがって、MCAを均一に含有する常温でゲル状の本発明の潤滑剤を調製する場合、アミド化合物をその融点以上に昇温して潤滑油基油と液体状態で撹拌して均一混合物をつくる際に、該混合物が液体状態であるときにMCAの微細粒子を添加し、撹拌して均一に混合し、冷却し常温でゲル状の本発明の潤滑剤組成物を調製することができる。また、アミド化合物と潤滑油基油とを液体状態で混合するに先立って、予め液体の潤滑油基油に均一に混合させてから、アミド化合物と融点以上の温度で混合することによって調製することもできる。このようにして、MCAを均一に分散することにより、本発明の効果を享受することができる。また、MCAなどのトリアジン誘導体を調合するとき、トリアジン誘導体を調合する時点で、その他の添加剤も同時に混合することにより効率的調合することができる。   Therefore, when the gel-like lubricant of the present invention containing MCA uniformly is prepared, the amide compound is heated above its melting point and stirred in a liquid state with the lubricant base oil to form a uniform mixture. In addition, when the mixture is in a liquid state, fine particles of MCA are added, and the mixture is stirred and uniformly mixed, cooled, and a gel-like lubricant composition of the present invention can be prepared at room temperature. In addition, prior to mixing the amide compound and the lubricating base oil in a liquid state, the amide compound and the lubricating base oil are uniformly mixed with the liquid lubricating base oil in advance and then mixed at a temperature equal to or higher than the melting point. You can also. Thus, the effect of this invention can be enjoyed by disperse | distributing MCA uniformly. Further, when a triazine derivative such as MCA is prepared, it can be efficiently prepared by mixing other additives at the time of preparing the triazine derivative.

〔添加剤〕
本発明の潤滑剤組成物には、本発明の目的が損なわれない範囲で、より性能を向上させるために、従来からグリース、ゲル状潤滑剤、潤滑油などに用いられている、アルカリ土類金属系清浄剤、摩擦調整剤、摩耗防止剤、極圧剤、清浄分散剤、酸化防止剤、防錆剤、金属不活性化剤、消泡剤などの添加剤を添加することができる。特には、MoDTCなどのモリブデン化合物を微細なトリアジン誘導体を含有する本発明の潤滑剤組成物に添加すると、それらの相乗効果により、より一層摩擦係数を下げる効果があり、従来の技術を更に改善することが可能である。
〔Additive〕
In the lubricant composition of the present invention, alkaline earths that have been conventionally used for greases, gel lubricants, lubricating oils, etc., in order to further improve the performance within the range where the object of the present invention is not impaired. Additives such as metal detergents, friction modifiers, antiwear agents, extreme pressure agents, detergent dispersants, antioxidants, rust inhibitors, metal deactivators and antifoaming agents can be added. In particular, when a molybdenum compound such as MoDTC is added to the lubricant composition of the present invention containing a fine triazine derivative, there is an effect of further reducing the coefficient of friction due to their synergistic effect, further improving the conventional technique. It is possible.

アルカリ土類金属系清浄剤としては、マグネシウム、カルシウム、バリウム等のアルカリ土類金属を含有するもので、例えば、アルカリ土類金属スルホネート、アルカリ土類金属フェネート、アルカリ土類金属サリシレートなどが挙げられる。摩擦調整剤としては脂肪族アミン、脂肪族アミド、脂肪族イミド、アルコール、エステル、リン酸エステルアミン塩、亜リン酸エステルアミン塩など、摩耗防止剤としてはリン酸エステル、ジアルキルジチオリン酸亜鉛など、極圧剤としては硫化オレフィン、硫化油脂など、分散剤としてはポリアルケニルコハク酸イミド、ポリアルケニルコハク酸エステルおよびそれぞれのホウ酸変性物など、酸化防止剤としてはアミン系、フェノール系の酸化防止剤など、金属不活性化剤としてはベンゾトリアゾールなど、防錆剤としてはアルケニルコハク酸エステルまたは部分エステルなど、消泡剤としてはシリコーン化合物、エステル系消泡剤などがそれぞれ挙げられる。   The alkaline earth metal detergent contains an alkaline earth metal such as magnesium, calcium, barium, and examples thereof include alkaline earth metal sulfonate, alkaline earth metal phenate, alkaline earth metal salicylate, and the like. . Examples of friction modifiers include aliphatic amines, aliphatic amides, aliphatic imides, alcohols, esters, phosphate ester amine salts, phosphite ester amine salts, and antiwear agents such as phosphate esters and zinc dialkyldithiophosphates. Extreme pressure agents such as sulfurized olefins and sulfurized fats and oils, dispersants such as polyalkenyl succinimides, polyalkenyl succinic acid esters and their respective boric acid modifications, antioxidants such as amine-based and phenol-based antioxidants Examples of the metal deactivator include benzotriazole, examples of the rust preventive include alkenyl succinic acid ester or partial ester, and examples of the antifoaming agent include a silicone compound and an ester-based antifoaming agent.

また特には、モリブデンを含有する有機モリブデン化合物、二硫化モリブデンなどを併用することで、より一層潤滑性能を向上した潤滑剤組成物を得ることができる。有機モリブデン化合物としては、モリブデンジチオカーバメート(MoDTC)やモリブデンジチオフォスフェート(MoDTP)などが挙げられる。二硫化モリブデンは、固体潤滑剤として一般的に知られているものを使用することができる。MoDTC、MoDTP、二硫化モリブデンは、MCAと同様の調合により、ゲル状潤滑剤中に安定に分散化することが可能である。また、モリブデン化合物の配合量は、モリブデン原子(Mo)として潤滑剤組成物全体に対する質量割合で、0.1〜10質量%含有されることが好ましく、より好ましくは0.2〜3質量%である。     In particular, by using an organic molybdenum compound containing molybdenum, molybdenum disulfide, or the like in combination, a lubricant composition with further improved lubricating performance can be obtained. Examples of the organic molybdenum compound include molybdenum dithiocarbamate (MoDTC) and molybdenum dithiophosphate (MoDTP). As the molybdenum disulfide, those generally known as solid lubricants can be used. MoDTC, MoDTP, and molybdenum disulfide can be stably dispersed in the gel lubricant by the same formulation as MCA. Further, the compounding amount of the molybdenum compound is preferably 0.1 to 10% by mass, more preferably 0.2 to 3% by mass, as a molybdenum atom (Mo), in a mass ratio with respect to the entire lubricant composition. is there.

〔潤滑システム〕
本発明の潤滑剤組成物は、常温でゲル状の熱可逆性を有するので、摺動部分が作動時には摩擦熱によって液体状となって摺動部に浸入して潤滑油膜を形成し、停止時には摺動部の温度が低下して常温になり、潤滑剤組成物は半固体状になる。したがって、従来、グリースが使われている、精密機械、産業機械、輸送機械、測定機器などの機械システムにおける各種軸受、歯車、ピストンシリンダー、駆動系などの様々な摺動部やグリースでは特性が充分でない特殊な機器、部品、条件下の摺動部に、本発明の潤滑剤組成物を充填または塗布することにより、潤滑システムを構成することができる。
[Lubrication system]
Since the lubricant composition of the present invention has a gel-like thermoreversibility at normal temperature, the sliding portion becomes liquid by frictional heat when operating and enters the sliding portion to form a lubricating oil film, and when stopped The temperature of the sliding part is lowered to normal temperature, and the lubricant composition becomes semisolid. Therefore, various sliding parts and greases such as various bearings, gears, piston cylinders, drive systems, etc. in mechanical systems such as precision machinery, industrial machinery, transport machinery, and measuring equipment that have been used with grease have sufficient characteristics. A lubricating system can be configured by filling or applying the lubricant composition of the present invention to a sliding part under non-special equipment, parts and conditions.

以下、実施例および比較例に基づいてより本発明をより詳細に説明するが、本発明はかかる実施例に限定されるものではない。     EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this Example.

〔潤滑剤組成物の調製〕
次に示す潤滑油基油、ゲル化剤、MCA及び添加剤を用いて実施例及び比較例の潤滑剤組成物を調製した。
(A)潤滑油基油:
(A1)PAO(動粘度(40℃):400mm/s、粘度指数:150、流動点:−35℃、引火点:280℃)
(A2)鉱物油(動粘度(40℃):22mm/s、粘度指数:125、流動点:−15℃、引火点:230℃)
(A3)菜種油(動粘度(40℃):32mm/s、粘度指数:200、流動点:−25℃、引火点:330℃)
(B)ゲル化剤:
(B1)ビスアミド(エチレンビスステアリルビスアミド、融点150℃)
(B2)モノアミド(N−ステアリルステアリン酸アミド、融点95℃)
(C)添加剤:
(C1)トリクレジルフォスフェート(TCP)
(C2)モリブデンジチオカーバメート(MoDTC)
(C3)モリブデンジチオフォスフェート(MoDTP)
(C4)二硫化モリブデン(MoS、平均粒子径1μm)
(D)メラミンシアヌレート(MCA、堺化学工業製、STABIACE MC−5S、平均粒径=0.5μm)
(E)Li石けん:12ヒドロキシステアリン酸リチウム
(Preparation of lubricant composition)
The lubricant compositions of Examples and Comparative Examples were prepared using the following lubricant base oil, gelling agent, MCA, and additives.
(A) Lubricating base oil:
(A1) PAO (kinematic viscosity (40 ° C.): 400 mm 2 / s, viscosity index: 150, pour point: −35 ° C., flash point: 280 ° C.)
(A2) Mineral oil (kinematic viscosity (40 ° C.): 22 mm 2 / s, viscosity index: 125, pour point: −15 ° C., flash point: 230 ° C.)
(A3) Rapeseed oil (kinematic viscosity (40 ° C.): 32 mm 2 / s, viscosity index: 200, pour point: −25 ° C., flash point: 330 ° C.)
(B) Gelling agent:
(B1) Bisamide (ethylenebisstearylbisamide, melting point 150 ° C.)
(B2) Monoamide (N-stearyl stearamide, melting point 95 ° C.)
(C) Additive:
(C1) tricresyl phosphate (TCP)
(C2) Molybdenum dithiocarbamate (MoDTC)
(C3) Molybdenum dithiophosphate (MoDTP)
(C4) Molybdenum disulfide (MoS 2 , average particle size 1 μm)
(D) Melamine cyanurate (MCA, manufactured by Sakai Chemical Industry, STABIACE MC-5S, average particle size = 0.5 μm)
(E) Li soap: 12 hydroxy lithium stearate

実施例および比較例で使用した潤滑剤組成物を、上記A〜Dの各成分を用い、表1に示す配合割合(組成物全量基準での質量%)で次のようにしてブレンドし調製した。
(A1)〜(A3)の潤滑油基油を投入した撹拌混合器(ホットプレートスターラー)に(B1)から(B2)のゲル化剤を加えて、融点以上に昇温してゲル化剤を溶融し液体の状態で均一に混ざり合うまで撹拌した。そこに(C1)〜(C4)の添加剤と(D)のMCAを加えてさらに1時間撹拌した。その後、加熱と撹拌を停止し、そのまま放置して室温にまで降温し、実施例1〜7、及び比較例1、2の潤滑剤組成物を得た。比較例3は、Liせっけんを増ちょう剤としたグリースで、MCAを所定量混合し、25℃(半固体状)で1時間混練して調製した。
The lubricant compositions used in the examples and comparative examples were blended and prepared as follows using the components A to D described above at a blending ratio shown in Table 1 (mass% based on the total amount of the composition). .
The gelling agent (B1) to (B2) is added to the stirring mixer (hot plate stirrer) charged with the lubricating base oil of (A1) to (A3), and the gelling agent is heated up to the melting point or higher. It stirred until it melted and mixed uniformly in a liquid state. The additives (C1) to (C4) and the MCA (D) were added thereto, and the mixture was further stirred for 1 hour. Thereafter, the heating and stirring were stopped, and the mixture was left as it was and cooled to room temperature. Thus, the lubricant compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were obtained. Comparative Example 3 was a grease using Li soap as a thickener, and was prepared by mixing a predetermined amount of MCA and kneading at 25 ° C. (semi-solid state) for 1 hour.

このようにして得た、実施例1〜7及び比較例1〜3の潤滑剤組成物それぞれについて、外観、ちょう度(不混和ちょう度、混和ちょう度、ちょう度差)、潤滑性能(焼付荷重、摩耗量)を測定、評価した。得られた測定・評価結果を表1下部に示す。
For each of the lubricant compositions of Examples 1 to 7 and Comparative Examples 1 to 3 thus obtained, the appearance, consistency (immiscibility consistency, mixing consistency, consistency of consistency), lubrication performance (seizure load) , Wear amount) was measured and evaluated. The obtained measurement / evaluation results are shown in the lower part of Table 1.

Figure 2009153938
Figure 2009153938

〔測定・評価方法〕
前記の測定及び評価は、次の方法にて行った。
[Measurement and evaluation method]
The measurement and evaluation were performed by the following method.

〔外観〕
規定の配合割合で調合し、室温まで冷却した後、組成物の出来上がりを外観目視により観察した。析出物や沈殿物が発生し、均一な組成物が得られなかった場合を不合格とし、均一ゲルが得られた場合を合格と記録した。
〔appearance〕
After blending at a prescribed blending ratio and cooling to room temperature, the finished composition was visually observed. A case where a precipitate or a precipitate was generated and a uniform composition was not obtained was rejected, and a case where a uniform gel was obtained was recorded as acceptable.

〔ちょう度〕
JIS K2220に従い、1/4ちょう度計にて不混和ちょう度、混和ちょう度を測定した。なお混和ちょう度から不混和ちょう度を差し引いた数値(ちょう度差)で、せん断安定性を評価した。数値が小さいほどせん断安定性が高く、より好ましい組成物と言える。
[Consistency]
According to JIS K2220, the immiscible penetration and the penetration consistency were measured with a ¼ consistency meter. The shear stability was evaluated by a value obtained by subtracting the immiscible consistency from the miscibility (concentration difference). The smaller the numerical value, the higher the shear stability, and it can be said that the composition is more preferable.

〔FALEX極圧性試験〕
ピン/ブロックタイプのFALEX摩擦試験機を用いて、実施例及び比較例の潤滑剤組成物の焼付荷重を測定した。
試験条件は、ASTM D3233に準拠し、より油膜ができにくく、厳しい潤滑条件をシミュレートすべく、回転数を低速の60rpmとし、室温で試験を開始した。また極少量での油剤での潤滑保持性能を確認するために、Vブロック部分に供試油剤を塗布して測定を行った。連続的に荷重を上げていき、焼付による異音、振動が確認された時点を焼付荷重(kgf)として記録した。
[FALEX extreme pressure test]
Using a pin / block type FALEX friction tester, the seizure loads of the lubricant compositions of Examples and Comparative Examples were measured.
The test conditions were based on ASTM D3233, and it was difficult to form an oil film, and in order to simulate severe lubrication conditions, the test was started at room temperature at a low speed of 60 rpm. In addition, in order to confirm the lubrication retention performance with a very small amount of oil, the test oil was applied to the V block portion and measured. The load was continuously increased, and the point in time when abnormal noise and vibration due to seizure were confirmed was recorded as seizure load (kgf).

〔FALEX耐摩耗性試験〕
上記と同じFALEX試験機を用い、以下の条件で耐摩耗性の評価を実施した。回転数60rpm、荷重540kgf、試験時間40minで潤滑し、摩耗量(ピン+ブロックの総和、mg)を測定した。
[FALEX abrasion resistance test]
Wear resistance was evaluated under the following conditions using the same FALEX testing machine as described above. Lubricating was performed at a rotational speed of 60 rpm, a load of 540 kgf, and a test time of 40 min, and the amount of wear (total of pin + block, mg) was measured.

表1に示す比較例1は、アミド系ゲル化剤を配合しておらず、そのためMCA、二硫化モリブデンが沈降・分離し、不均一な組成物となり、潤滑性が低い(焼付荷重が750kgfと低く、摩耗量が46mgと多い)結果を示した。また比較例2は、MCAを配合していない組成物であるが、均一なゲルが形成されているものの、焼付荷重が675kgf、摩耗量が60mgであり、潤滑性能としては不十分であった。またLiグリースにMCAを配合したものは、焼付荷重が725kgf、摩耗量が52mgであり、潤滑性能としては未だ十分とは言えなかった。   Comparative Example 1 shown in Table 1 does not contain an amide-based gelling agent. Therefore, MCA and molybdenum disulfide settle and separate, resulting in a non-uniform composition and low lubricity (the seizure load is 750 kgf). The result is low and the wear amount is as large as 46 mg). Further, Comparative Example 2 was a composition not containing MCA, and although a uniform gel was formed, the seizure load was 675 kgf and the wear amount was 60 mg, and the lubrication performance was insufficient. In addition, when LiCA was blended with MCA, the seizure load was 725 kgf and the wear amount was 52 mg, and the lubrication performance was still not sufficient.

一方、表1に示す実施例はいずれも焼付荷重が高く、摩耗量が少なく、良好な結果をしました。これらのうち、基油にPAOを用いた組成物では、比較例2に比べ、焼付荷重が高く、かつ摩耗量も少なく、優れた潤滑性能を示した。特にモリブデン化合物を併用した場合、より高い潤滑性能が示された。また低粘度鉱物油や植物油を基油とした実施例においても同様の高い潤滑性能が認められた。さらにMCAを配合することにより、混和ちょう度と不混和ちょう度の差が少なく、せん断安定性が向上した。
このように、微細な粒径を有するMCAを熱可逆性ゲル状潤滑剤に配合することにより焼付荷重が増加し、かつ摩耗量が少なくできることが分かる。
On the other hand, all of the examples shown in Table 1 showed good results with a high seizure load and little wear. Among these, in the composition using PAO as the base oil, the seizure load was high and the wear amount was small as compared with Comparative Example 2, and excellent lubrication performance was exhibited. In particular, when a molybdenum compound was used in combination, higher lubrication performance was shown. The same high lubrication performance was also observed in the examples based on low-viscosity mineral oil and vegetable oil. Further, by blending MCA, the difference between the penetration consistency and the immiscibility consistency was small, and the shear stability was improved.
Thus, it can be seen that by adding MCA having a fine particle size to the thermoreversible gel lubricant, the seizure load increases and the wear amount can be reduced.

本発明の潤滑剤組成物は、摩耗が顕著に低減され、かつ摩擦係数も低く安定する特性を有するため、精密機械、産業機械、輸送機械、測定機器などの機械システムにおける各種軸受、歯車、ピストンシリンダー、駆動系などの様々な摺動部に用いることができる。これにより、潤滑条件の厳しい機械システムの長寿命化に貢献し、かつ低く安定した摩擦係数の特性から省エネルギーにも寄与することができる。   Since the lubricant composition of the present invention has the characteristics that wear is remarkably reduced and the coefficient of friction is low and stable, various bearings, gears, and pistons in mechanical systems such as precision machinery, industrial machinery, transportation machinery, and measuring equipment. It can be used for various sliding parts such as cylinders and drive systems. This contributes to extending the life of mechanical systems with severe lubrication conditions, and also contributes to energy saving due to the low and stable characteristics of the friction coefficient.

Claims (6)

鉱油系、合成油系及び/又は動植物油系の潤滑油基油に、アミド化合物を1〜70質量%及びトリアジン誘導体を0.1〜50質量%含有することを特徴とする常温でゲル状の潤滑剤組成物。   A mineral base oil, synthetic oil base and / or animal and vegetable base oil base oil contains 1 to 70% by weight of an amide compound and 0.1 to 50% by weight of a triazine derivative. Lubricant composition. トリアジン誘導体が、メラミンシアヌレート(MCA)である請求項1に記載の潤滑剤組成物。   The lubricant composition according to claim 1, wherein the triazine derivative is melamine cyanurate (MCA). 潤滑油基油は、40℃における動粘度が5〜1000mm/sである請求項1又は2に記載の潤滑剤組成物。The lubricant composition according to claim 1, wherein the lubricating base oil has a kinematic viscosity at 40 ° C. of 5 to 1000 mm 2 / s. ちょう度が90〜400である請求項1〜3のいずれかに記載の潤滑剤組成物。   The lubricant composition according to any one of claims 1 to 3, which has a consistency of 90 to 400. さらに、モリブデン化合物をモリブデン(Mo)として0.1〜10質量%含有する請求項1〜4のいずれかに記載の潤滑剤組成物。   Furthermore, the lubricant composition in any one of Claims 1-4 which contains a molybdenum compound 0.1 to 10 mass% as molybdenum (Mo). 請求項1〜5のいずれかに記載の潤滑剤組成物を用いることを特徴とする潤滑システム。
A lubrication system using the lubricant composition according to claim 1.
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