JP2011195734A - Lubricating oil composition for internal combustion engine - Google Patents

Lubricating oil composition for internal combustion engine Download PDF

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JP2011195734A
JP2011195734A JP2010064942A JP2010064942A JP2011195734A JP 2011195734 A JP2011195734 A JP 2011195734A JP 2010064942 A JP2010064942 A JP 2010064942A JP 2010064942 A JP2010064942 A JP 2010064942A JP 2011195734 A JP2011195734 A JP 2011195734A
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mass
lubricating oil
internal combustion
viscosity
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JP5727713B2 (en
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Akira Yamada
亮 山田
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to JP2010064942A priority Critical patent/JP5727713B2/en
Priority to US13/635,593 priority patent/US20130029892A1/en
Priority to TW100109488A priority patent/TW201144427A/en
Priority to CN2011800117221A priority patent/CN102782107A/en
Priority to PCT/JP2011/056626 priority patent/WO2011115265A1/en
Priority to BR112012023571A priority patent/BR112012023571A2/en
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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
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    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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Abstract

PROBLEM TO BE SOLVED: To provide a lubricating oil composition for internal combustion engines that has low viscosity and nevertheless reduces noise while running, suppresses fatigue damage such as gear pitting, reduces oil consumption, and has good fuel efficiency.SOLUTION: The lubricating oil composition for internal combustion engines is obtained by blending, based on the total amount of the composition, 0.1-10 mass% of (A) a 2-20C olefin polymer having a mass-average molecular weight of 500-10,000 and/or (B) a polymer compound having a mass-average molecular weight of 10,000 or more and less than 100,000 with base oil having a viscosity index of 125 or more and Noack evaporation loss (250°C×1h) of 15 mass% or less, wherein (C) the blending amount of a polymer compound having a mass-average molecular weight of 100,000 or more is less than 1.0 mass%.

Description

本発明は,内燃機関用潤滑油組成物に関し,さらに詳しくは、走行時の騒音を低減し、疲労寿命を高め、オイル消費を低減し、かつ、良好な省燃費性を有する、二輪車用4サイクルエンジン用潤滑油としても有用な内燃機関用潤滑油組成物に関する。   The present invention relates to a lubricating oil composition for an internal combustion engine, and more specifically, a four-cycle for a motorcycle that has reduced noise during running, increased fatigue life, reduced oil consumption, and good fuel economy. The present invention relates to an internal combustion engine lubricating oil composition that is also useful as an engine lubricating oil.

省エネルギー、二酸化炭素(CO2)低減の要請などにより、内燃機関用潤滑油(エンジンオイル)においても必要な性能として省燃費性が強く求められている。
従来、四輪車に用いられるエンジンオイルについて、省燃費性を高める手段として、エンジンオイルを低粘度化することが行われてきた。
しかし、同じエンジンオイルであっても、二輪車に用いられるエンジンオイルの省燃費性を高めるために、エンジンオイルを低粘度化すると、四輪車と二輪車の機械的構造の相違から、種々の問題が発生する。
つまり、二輪車は、エンジンなどの装置を小型化する必要があるため、通常、エンジンとともに変速用トランスミッションをも同一のエンジンオイルで潤滑する構造を有している。
このような構造を有する二輪車に用いられるエンジンオイルとして、省燃費性を高めるために低粘度化したエンジンオイルを用いると、変速用トランスミッションでギヤピッチングなどの疲労損傷が発生する。また、二輪車では、エンジンがむき出しに設置されていることから、エンジン騒音が大きくなり騒音問題となる。さらに、二輪車は、エンジンが小型であることから、四輪車に比較して、オイルが高温になるため、オイルの蒸発に起因するオイル消費が大きくなる。
したがって、二輪車に用いるエンジン油を低粘度化して省燃費性を向上させようとした場合、これらの問題を解決する必要がある。
Due to demands for energy saving, carbon dioxide (CO 2 ) reduction, etc., fuel efficiency is strongly demanded as a necessary performance even in lubricating oil for internal combustion engines (engine oil).
Conventionally, with respect to engine oil used in four-wheeled vehicles, reducing the viscosity of engine oil has been performed as a means for improving fuel economy.
However, even with the same engine oil, reducing the viscosity of the engine oil in order to improve the fuel efficiency of the engine oil used in motorcycles causes various problems due to the difference in mechanical structure between the four-wheeled vehicle and the two-wheeled vehicle. appear.
In other words, since it is necessary to downsize the engine and other devices, the two-wheeled vehicle usually has a structure in which the transmission for transmission as well as the engine is lubricated with the same engine oil.
When engine oil having a low viscosity is used as an engine oil used for a motorcycle having such a structure in order to improve fuel efficiency, fatigue damage such as gear pitching occurs in the transmission for transmission. Further, in a motorcycle, since the engine is exposed, the engine noise becomes large, which causes a noise problem. Furthermore, since the two-wheeled vehicle has a small engine, the oil is hotter than the four-wheeled vehicle, and the oil consumption due to the evaporation of the oil increases.
Therefore, it is necessary to solve these problems when attempting to improve fuel economy by reducing the viscosity of engine oil used in motorcycles.

また、従来、実使用温度領域の粘度を下げる手段として、基油に高分子化合物である粘度指数向上剤を組み合わせて粘度指数を向上させることが行われている(例えば、特許文献1参照)。しかし、粘度指数向上剤を含む潤滑油は、エンジンの軸受や歯車の歯面などの高せん断下では、高分子の配向により、粘度低下を起こす。そのために、従来のマルチグレード型エンジンオイル(高分子化合物を含む潤滑油)では、高温高せん断粘度が不足するため耐金属疲労性が低下する傾向があり、二輪車に用いるエンジン油を低粘度化する上で障害になっている。
したがって、二輪車に用いるエンジン油を低粘度化して省燃費性を向上させようとした場合のこの種の問題も解決できないのが現状である。
Conventionally, as a means for lowering the viscosity in the actual use temperature range, a viscosity index is improved by combining a base oil with a viscosity index improver that is a polymer compound (see, for example, Patent Document 1). However, a lubricating oil containing a viscosity index improver causes a decrease in viscosity due to the orientation of the polymer under high shear such as engine bearings and gear tooth surfaces. For this reason, conventional multi-grade engine oils (lubricants containing polymer compounds) tend to have low metal fatigue resistance due to insufficient high-temperature and high-shear viscosity, and lower the engine oil used for motorcycles. It is an obstacle on the top.
Therefore, the present situation is that it is not possible to solve this type of problem when attempting to improve fuel economy by reducing the viscosity of engine oil used in motorcycles.

特開2000−087070号公報JP 2000-087070 A

本発明は、このような状況下で、低粘度であっても走行時の騒音を低減し、ギヤピッチングなどの疲労損傷を抑制し、オイル消費を低減し、かつ、良好な省燃費性を有する内燃機関用潤滑油組成物を提供することを目的とするものである。   Under such circumstances, the present invention reduces noise during running even at low viscosity, suppresses fatigue damage such as gear pitching, reduces oil consumption, and has good fuel economy. An object of the present invention is to provide a lubricating oil composition for an internal combustion engine.

本発明者らは、鋭意研究を重ねた結果、特定の基油に、特定構造及び分子量を有する重合体、及び/又は特定分子量の高分子化合物を配合することにより、その目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。すなわち、本発明は、   As a result of extensive research, the present inventors can achieve the object by blending a specific base oil with a polymer having a specific structure and molecular weight and / or a polymer compound with a specific molecular weight. I found. The present invention has been completed based on such findings. That is, the present invention

[1] 粘度指数が125以上であり、Noack蒸発量(250℃×1h)が15質量%以下である基油に、組成物全量を基準として、(A)質量平均分子量500以上10,000以下の炭素数2〜20のオレフィン重合体、及び/又は(B)質量平均分子量が10,000以上100,000未満の高分子化合物を0.1〜10質量%含み、(C)質量平均分子量100,000以上の高分子化合物の配合量が1.0質量%未満であることを特徴とする内燃機関用潤滑油組成物、
[2]前記高分子化合物が、ポリメタクリレート、オレフィン共重合体、スチレン共重合体、及び、ポリイソブチレンの中から選ばれる一種又は二種以上の高分子化合物である上記[1]に記載の内燃機関用潤滑油組成物、
[3]さらに、モリブデン系摩擦調整剤若しくは無灰系摩擦調整剤を配合したことを特徴とする上記[1]又は[2]に記載の内燃機関用潤滑油組成物、
[4]Noack蒸発量(250℃×1h)が10.0質量%以下であり、かつ、粘度指数が140以上である上記[1]〜[3]のいずれかに記載の内燃機関用潤滑油組成物、
[5]二輪車用4サイクルエンジン用潤滑油である上記[1]〜[4]のいずれかに記載の内燃機関用潤滑油組成物、
を提供するものである。
[1] To a base oil having a viscosity index of 125 or more and a Noack evaporation (250 ° C. × 1 h) of 15% by mass or less, based on the total amount of the composition, (A) a mass average molecular weight of 500 to 10,000 Containing 0.1 to 10% by mass of a C 2-20 olefin polymer and / or (B) a polymer compound having a mass average molecular weight of 10,000 or more and less than 100,000, and (C) a mass average molecular weight of 100. A lubricating oil composition for an internal combustion engine, wherein the blending amount of the polymer compound of 1,000 or more is less than 1.0% by mass,
[2] The internal combustion according to [1], wherein the polymer compound is one or two or more polymer compounds selected from polymethacrylate, olefin copolymer, styrene copolymer, and polyisobutylene. Lubricating oil composition for engine,
[3] The lubricating oil composition for internal combustion engines according to the above [1] or [2], further comprising a molybdenum friction modifier or an ashless friction modifier,
[4] The lubricating oil for internal combustion engines according to any one of [1] to [3], wherein the Noack evaporation amount (250 ° C. × 1 h) is 10.0% by mass or less and the viscosity index is 140 or more. Composition,
[5] The lubricating oil composition for internal combustion engines according to any one of the above [1] to [4], which is a lubricating oil for a four-cycle engine for a motorcycle.
Is to provide.

本発明によれば、低粘度であっても走行時の騒音を低減し、ギヤピッチングなどの疲労損傷を抑制し、オイル消費を低減し、かつ、良好な省燃費性を有する内燃機関用潤滑油組成物を提供することができる。   According to the present invention, a lubricating oil for an internal combustion engine that reduces noise during traveling, suppresses fatigue damage such as gear pitching, reduces oil consumption, and has good fuel economy even with low viscosity. A composition can be provided.

本発明の内燃機関用潤滑油組成物(以下、「本組成物」ともいう)は、粘度指数が125以上であり、Noack蒸発量(250℃×1h)が15質量%以下である基油に、組成物全量を基準として、(A)質量平均分子量500以上10,000以下の炭素数2〜20のオレフィン重合体、及び/又は(B)質量平均分子量が10,000以上100,000未満の高分子化合物を0.1〜10質量%配合してなり、(C)質量平均分子量100,000以上の高分子化合物の配合量が1.0質量%未満であることを特徴とする内燃機関用潤滑油組成物である。以下、本組成物について詳細に説明する。   The lubricating oil composition for internal combustion engines of the present invention (hereinafter also referred to as “the present composition”) is a base oil having a viscosity index of 125 or more and a Noack evaporation (250 ° C. × 1 h) of 15 mass% or less. Based on the total amount of the composition, (A) an olefin polymer having 2 to 20 carbon atoms having a mass average molecular weight of 500 to 10,000, and / or (B) having a mass average molecular weight of 10,000 to less than 100,000. For internal combustion engines, comprising 0.1 to 10% by mass of a polymer compound, and (C) the compounding amount of a polymer compound having a mass average molecular weight of 100,000 or more is less than 1.0% by mass. It is a lubricating oil composition. Hereinafter, the composition will be described in detail.

1.基油
本発明で用いる基油は、鉱物油、合成油又はそれらの混合物からなる潤滑油基油であり、その粘度指数が125以上であることを要する。基油の粘度指数が高いほど、内燃機関用潤滑油組成物の高温における粘度の低下を抑制し、耐摩耗性や疲労寿命の低下を抑制することができる。粘度指数は130以上であることがより好ましい。
なお、粘度指数は、JIS K 2283に準拠して測定された値である。
また、本発明で用いる基油は、Noack蒸発量(250℃×1h)が15質量%以下であることが必要である。Noack蒸発量(250℃×1h)が15質量%を超えると、本組成物の蒸発損失によるオイル消費が増大する。Noack蒸発量は、10質量%以下が好ましい。
なお、Noack蒸発量は、CEC−L−40−A−93、ASTM D5800に規定の方法で測定した値である。
1. Base oil The base oil used in the present invention is a lubricating base oil composed of mineral oil, synthetic oil, or a mixture thereof, and the viscosity index is required to be 125 or more. The higher the viscosity index of the base oil, the lower the viscosity of the lubricating oil composition for internal combustion engines at high temperatures, and the lower the wear resistance and fatigue life. The viscosity index is more preferably 130 or more.
The viscosity index is a value measured according to JIS K 2283.
The base oil used in the present invention is required to have a Noack evaporation (250 ° C. × 1 h) of 15% by mass or less. When the Noack evaporation amount (250 ° C. × 1 h) exceeds 15% by mass, oil consumption due to evaporation loss of the composition increases. The Noack evaporation is preferably 10% by mass or less.
The Noack evaporation amount is a value measured by a method defined in CEC-L-40-A-93 and ASTM D5800.

また、基油としては、環分析による%CAが3.0以下で、硫黄分の含有量が100質量ppm以下のものが好ましく用いられる。
ここで、環分析による%CAとは、環分析n−d−M法にて算出した芳香族分の割合(百分率)を示す。また、硫黄分はJIS K 2541に準拠して測定した値である。
%CAが3.0以下で、硫黄分が100質量ppm以下の基油は、良好な酸化安定性を有し、酸価の上昇やスラッジの生成を抑制しうる潤滑油組成物を提供することができる。より好ましい%CAは1.0以下、さらには0.5以下である。
As the base oil, in% by ring analysis C A of 3.0 or less, the sulfur content is include: 100 ppm by mass is preferably used.
Here, the% C A by ring analysis shows a proportion of aromatic content calculated by ring analysis n-d-M method (percentage). The sulfur content is a value measured according to JIS K2541.
A base oil having a% CA of 3.0 or less and a sulfur content of 100 mass ppm or less provides a lubricating oil composition having good oxidation stability and capable of suppressing an increase in acid value and sludge formation. be able to. More preferable% C A is 1.0 or less, and further 0.5 or less.

本組成物に使用される基油は、100℃において、2〜20mm2/sの動粘度を有することが好ましく、より好ましい動粘度は3〜15mm2/sの範囲であり、さらに好ましい動粘度は3.5〜10mm2/sの範囲である。基油の動粘度が高すぎると、組成物としたときに攪拌抵抗が大きくなり、また、流体潤滑域での摩擦係数が高くなるため、省燃費特性が悪化する。また、動粘度が低すぎると、内燃機関の動弁系、ピストン、リングや軸受等の摺動部において摩耗が増加する。 The base oil used in the composition preferably has a kinematic viscosity of 2 to 20 mm 2 / s at 100 ° C., more preferably a kinematic viscosity in the range of 3 to 15 mm 2 / s, and even more preferable kinematic viscosity. Is in the range of 3.5 to 10 mm 2 / s. When the kinematic viscosity of the base oil is too high, the stirring resistance is increased when the composition is used, and the coefficient of friction in the fluid lubrication region is increased, so that the fuel saving characteristics are deteriorated. On the other hand, if the kinematic viscosity is too low, wear increases in sliding parts such as valve systems, pistons, rings and bearings of internal combustion engines.

前記鉱物油としては、例えば、原油を常圧蒸留して得られる潤滑油留分や常圧残油を減圧蒸留して得られる潤滑油留分を、溶剤脱れき、溶剤抽出、溶剤脱ろう、接触脱ろう、水素化精製、水素化分解などの1つ以上の処理を行って精製したもの、或いは鉱油系ワックスやフィッシャー・トロプシュプロセス等により製造されるワックス(GTLワックス)を異性化することによって製造される鉱物油などが挙げられる。   As the mineral oil, for example, a lubricating oil fraction obtained by atmospheric distillation of a crude oil or a lubricating oil fraction obtained by vacuum distillation of an atmospheric residual oil, solvent removal, solvent extraction, solvent dewaxing, By isomerizing a wax refined by one or more treatments such as catalytic dewaxing, hydrorefining, hydrocracking, or a wax produced by a mineral oil-based wax or a Fischer-Tropsch process (GTL wax) Examples include manufactured mineral oils.

特に、本発明における粘度指数が125以上の基油は、潤滑油留分の水素化分解、あるいはワックスの水素異性化で得られた生成油を溶剤脱ろう又は水素化脱ろうすることにより好ましく製造することができる。
水素化分解は、通常、上記潤滑油留分を、水素化分解触媒、例えば、シリカ−アルミナ担体上にニッケル、コバルト等の8族金属の1種以上、及び、モリブデン、タングステン等の6A族金属の1種以上を担持した触媒と、水素分圧7〜14MPaの水素存在下、350〜450℃の温度、0.1〜2hr-1のLHSV(液空間速度)で接触させて行われる。
また、ワックスの水素異性化は、例えば、鉱油系潤滑油の溶剤脱ろう工程で得られるスラックワックスやフィッシャー・トロプシュ合成で得られたワックス等を、水素異性化触媒、例えばアルミナ、或いはシリカ−アルミナ担体上にニッケル、コバルト等の8族金属、及びモリブデン、タングステン等の6A族金属の1種以上を担持した触媒やゼオライト触媒もしくはゼオライト含有担体に白金等を担持した触媒と、水素分圧5〜14MPaの水素存在下、300〜450℃の温度、0.1〜2hr-1のLHSV(液空間速度)で接触させて行われる。
In particular, a base oil having a viscosity index of 125 or more in the present invention is preferably produced by solvent dewaxing or hydrodewaxing a product oil obtained by hydrocracking a lubricating oil fraction or hydroisomerizing a wax. can do.
In hydrocracking, the above-mentioned lubricating oil fraction is usually separated from a hydrocracking catalyst such as one or more group 8 metals such as nickel and cobalt on a silica-alumina carrier, and a group 6A metal such as molybdenum and tungsten. In the presence of hydrogen having a hydrogen partial pressure of 7 to 14 MPa and a temperature of 350 to 450 ° C. and an LHSV (liquid space velocity) of 0.1 to 2 hr −1 .
Also, the hydroisomerization of the wax may be performed by, for example, converting a slack wax obtained in a solvent dewaxing process of a mineral oil or a wax obtained by Fischer-Tropsch synthesis into a hydroisomerization catalyst such as alumina or silica-alumina. A catalyst in which one or more of group 8 metals such as nickel and cobalt and a group 6A metal such as molybdenum and tungsten are supported on a support, a zeolite catalyst or a catalyst in which platinum or the like is supported on a zeolite-containing support; In the presence of 14 MPa hydrogen, the contact is performed at a temperature of 300 to 450 ° C. and an LHSV (liquid space velocity) of 0.1 to 2 hr −1 .

上記方法で得られる水素化分解生成油や水素異性化生成油は、通常、軽質留分を留去して潤滑油留分を得るが、さらに脱ろう処理を行い、ワックス分を除去して、低流動点(例えば、−10℃以下)の潤滑油基油を得ることができる。
以上のような方法で得られた潤滑油留分は、所望により、さらに溶剤精製或いは水素化精製を行ってもよい。
The hydrocracked product oil and hydroisomerized product oil obtained by the above method are usually obtained by distilling off the light fraction to obtain a lubricating oil fraction, which is further dewaxed to remove the wax content, A lubricating base oil having a low pour point (eg, −10 ° C. or lower) can be obtained.
The lubricating oil fraction obtained by the above method may be further subjected to solvent purification or hydrorefining as desired.

一方、合成油としては、従来公知の種々のものが使用可能であり、例えば、ポリ−α−オレフィン、ポリブテン、ポリオールエステル、二塩基酸エステル、芳香族エステル、リン酸エステル、ポリフェニルエーテル、アルキルベンゼン、アルキルナフタレン、ポリオキシアルキレングリコール、ネオペンチルグリコール、シリコーンオイル、トリメチロールプロパン、ペンタエリスリトール、更にはヒンダードエステルなどを用いることができるが、特にポリ−α−オレフィンは粘度指数が比較的高い点、及び、鉱物油に近い組成であるため、従来の鉱物油で使用している添加剤をそのまま使用できる点で好ましい。
本発明で用いる基油は、上記性状を満たす限り、2種類以上の鉱物油、2種類以上の合成油の混合物、又は、鉱物油と合成油の混合物であっても差し支えなく、上記混合物における2種類以上の基油の混合比は、任意に選ぶことができる。
On the other hand, various known oils can be used as the synthetic oil. For example, poly-α-olefin, polybutene, polyol ester, dibasic acid ester, aromatic ester, phosphoric acid ester, polyphenyl ether, alkylbenzene. , Alkyl naphthalene, polyoxyalkylene glycol, neopentyl glycol, silicone oil, trimethylolpropane, pentaerythritol, and hindered ester can be used. Especially, poly-α-olefin has a relatively high viscosity index. And since it is a composition close to mineral oil, it is preferable at the point which can use the additive currently used with the conventional mineral oil as it is.
The base oil used in the present invention may be two or more kinds of mineral oils, a mixture of two or more kinds of synthetic oils, or a mixture of mineral oil and synthetic oil as long as the above properties are satisfied. The mixing ratio of more than one type of base oil can be arbitrarily selected.

2.オレフィン重合体及び高分子化合物
本発明の内燃機関用潤滑油組成物は、上述の基油に対して、(A)質量平均分子量500以上10,000以下の炭素数2〜20のオレフィン重合体、及び/又は(B)質量平均分子量が10,000以上100,000未満の高分子化合物を0.1〜10質量%、好ましくは0.3〜7質量%、より好ましくは0.5〜5質量%配合してなり、(C)質量平均分子量100,000以上の高分子化合物の配合量が1.0質量%未満とすることによって得られる。
質量平均分子量500以上10,000以下の炭素数2〜20のオレフィン重合体や質量平均分子量が10,000以上100,000未満の高分子化合物を配合することで、組成物の粘度指数を高めるのみならず、騒音の発生を抑制することができる。
基油に対して配合される上記(B)高分子化合物の質量平均分子量が100,000未満としたのは、基油に対して配合される高分子化合物の分子量が大きいほど粘度指数を向上させる効果は大きいものの、せん断によって高分子化合物の分子鎖が配向することで、一時的な粘度低下を引き起こし、必要な高温高せん断粘度を維持できなくなる恐れがあり、また、使用により高分子化合物の分子鎖が切断されて分子量が低下し、粘度が低下してしまう恐れがあるからである。
したがって、質量平均分子量が100,000以上(より好ましくは70,000以上、さらに好ましくは50,000以上)の上記(C)高分子化合物を配合しないことが望ましいのであるが、粘度指数を向上させるために止むを得ず添加する場合もある。ただし、その場合であっても1.0質量%未満、好ましくは0.1質量%未満、さらに好ましくは、0.01質量%未満とすることで、本発明の内燃機関用潤滑油組成物を得ることができる。
なお、上記(B)高分子化合物の質量平均分子量は70,000以下であることが好ましく、50,000以下であることが、より好ましい。
2. Olefin polymer and polymer compound The lubricating oil composition for an internal combustion engine of the present invention is (A) an olefin polymer having 2 to 20 carbon atoms having a mass average molecular weight of 500 to 10,000, And / or (B) 0.1 to 10% by mass, preferably 0.3 to 7% by mass, more preferably 0.5 to 5% by mass of the polymer compound having a mass average molecular weight of 10,000 or more and less than 100,000. %, And the amount of the polymer compound having a mass average molecular weight of 100,000 or more is less than 1.0% by mass.
By blending a olefin polymer having 2 to 20 carbon atoms having a mass average molecular weight of 500 to 10,000 and a polymer compound having a mass average molecular weight of 10,000 to less than 100,000, only the viscosity index of the composition is increased. In other words, the generation of noise can be suppressed.
The reason why the mass average molecular weight of the polymer compound (B) blended with the base oil is less than 100,000 is that the viscosity index improves as the molecular weight of the polymer compound blended with the base oil increases. Although the effect is large, the molecular chain of the polymer compound is oriented by shearing, which may cause a temporary decrease in viscosity and may not be able to maintain the required high temperature and high shear viscosity. This is because the chain may be cleaved to reduce the molecular weight and reduce the viscosity.
Therefore, it is desirable not to add the above-mentioned (C) polymer compound having a mass average molecular weight of 100,000 or more (more preferably 70,000 or more, more preferably 50,000 or more), but the viscosity index is improved. Therefore, it may be unavoidably added. However, even in that case, the lubricating oil composition for an internal combustion engine of the present invention can be obtained by making the amount less than 1.0% by mass, preferably less than 0.1% by mass, and more preferably less than 0.01% by mass. Obtainable.
In addition, it is preferable that the mass mean molecular weight of the said (B) polymer compound is 70,000 or less, and it is more preferable that it is 50,000 or less.

前記(A)のオレフィン重合体としては、炭素数2〜20、好ましくは2〜16、より好ましくは2〜14のオレフィンの単独重合体及び共重合体から選択される一種以上を使用する。炭素数2〜20のオレフィン重合体として代表的なものは、エチレン−α−オレフィン共重合体並びにα−オレフィンの単独重合体及び共重合体が挙げられる。このうち、エチレン−α−オレフィン共重合体としては、15〜80モル%のエチレンと、プロピレン、1−ブテン、1−デセンなどの炭素数3〜20のα−オレフィンとの共重合体が挙げられ、ランダム体でもブロック体でもよい。該共重合体は潤滑油に対して非分散型であるが、エチレン−α−オレフィン共重合体をマレイン酸、N−ビニルピロリドン、N−ビニルイミダゾール、グリシジルアクリレートなどでグラフト化した分散型のものも使用できる。また、α−オレフィンの単独重合体及び共重合体は、好ましくは炭素数4〜20、より好ましくは炭素数6〜16、さらに好ましくは炭素数6〜14のα−オレフィンの単独重合体及び共重合体で、共重合体は、ランダム体でもブロック体でもよい。
これらのオレフィン重合体は、任意の方法で製造することができる。例えば、無触媒による熱反応によって製造することができるほか、過酸化ベンゾイルなどの有機過酸化物触媒;塩化アルミニウム、塩化アルミニウム−多価アルコール系、塩化アルミニウム−四塩化チタン系、塩化アルミニウム−アルキル錫ハライド系、フッ化ホウ素などのフリーデルクラフツ型触媒;有機塩化アルミニウム−四塩化チタン系、有機アルミニウム−四塩化チタン系などのチーグラー型触媒;アルミノキサン−ジルコノセン系、イオン性化合物−ジルコノセン系などのメタロセン型触媒;塩化アルミニウム−塩基系、フッ化ホウ素−塩基系などのルイス酸コンプレックス型触媒などの公知の触媒系を用いて、上記のオレフィンを単独重合または共重合させることで製造することができる。なお、上記したオレフィン重合体を用いることができるが、当該オレフィン重合体は通常二重結合を有しているので、その熱・酸化安定性を考慮すると、オレフィン重合体中の二重結合を水素化したオレフィン重合体の水素化物を用いることが好ましい。
なお、オレフィン重合体の質量平均分子量は2,000〜9,000であることが好ましく、3,000〜8,000であることが、より好ましい。
As the olefin polymer (A), one or more selected from homopolymers and copolymers of olefins having 2 to 20, preferably 2 to 16, and more preferably 2 to 14 carbon atoms are used. Typical examples of the olefin polymer having 2 to 20 carbon atoms include an ethylene-α-olefin copolymer and an α-olefin homopolymer and copolymer. Among these, as an ethylene-alpha-olefin copolymer, the copolymer of 15-80 mol% ethylene and C3-C20 alpha olefins, such as propylene, 1-butene, and 1-decene, is mentioned. It may be a random body or a block body. The copolymer is non-dispersed with respect to lubricating oil, but is a dispersion type in which an ethylene-α-olefin copolymer is grafted with maleic acid, N-vinylpyrrolidone, N-vinylimidazole, glycidyl acrylate, etc. Can also be used. The α-olefin homopolymers and copolymers are preferably 4-20 carbon atoms, more preferably 6-16 carbon atoms, and even more preferably 6-14 carbon atoms α-olefin homopolymers and copolymers. The polymer may be a random body or a block body.
These olefin polymers can be produced by any method. For example, it can be produced by a non-catalytic thermal reaction, and an organic peroxide catalyst such as benzoyl peroxide; aluminum chloride, aluminum chloride-polyhydric alcohol, aluminum chloride-titanium tetrachloride, aluminum chloride-alkyltin Friedel-Crafts type catalysts such as halides and boron fluoride; Ziegler type catalysts such as organic aluminum chloride-titanium tetrachloride type, organic aluminum-titanium tetrachloride type; metallocenes such as aluminoxane-zirconocene type, ionic compound-zirconocene type The catalyst can be produced by homopolymerizing or copolymerizing the above olefin using a known catalyst system such as Lewis acid complex catalyst such as aluminum chloride-base system or boron fluoride-base system. Although the above-mentioned olefin polymer can be used, since the olefin polymer usually has a double bond, considering the thermal and oxidation stability, the double bond in the olefin polymer is hydrogenated. It is preferable to use a hydrogenated olefin polymer.
The mass average molecular weight of the olefin polymer is preferably 2,000 to 9,000, and more preferably 3,000 to 8,000.

前記高分子化合物としては、ポリメタクリレート(PMA)、オレフィン系共重合体(オレフィンコポリマー)、スチレン系共重合体(例えば、スチレン−ジエン水素化共重合体など)及びポリイソブチレンから選ばれる少なくともいずれか一種が好ましく挙げられる。ポリメタクリレートは、分散型、非分散型のどちらでも使用できる。オレフィンコポリマーとして代表的なものは、エチレン−α−オレフィン共重合体である。
これらの中から一種を単独で、あるいは二種以上組み合わせて使用することができる。より好ましくは、ポリメタクリレート(PMA)、オレフィン系共重合体(オレフィンコポリマー)が挙げられる。
The polymer compound is at least one selected from polymethacrylate (PMA), olefin copolymer (olefin copolymer), styrene copolymer (for example, styrene-diene hydrogenated copolymer) and polyisobutylene. One type is preferred. The polymethacrylate can be used in either a dispersion type or a non-dispersion type. A typical olefin copolymer is an ethylene-α-olefin copolymer.
One of these can be used alone or in combination of two or more. More preferably, a polymethacrylate (PMA) and an olefin copolymer (olefin copolymer) are used.

3.摩擦調整剤
また、本発明の内燃機関用潤滑油組成物においては、省燃費特性を向上させるために、モリブデン系摩擦調整剤や無灰系摩擦調整剤を配合することが好ましい。モリブデン系摩擦調整剤及び無灰系摩擦調整剤を併用するとより好ましい。
モリブデン系摩擦調整剤としては、ジチオカルバミン酸モリブデン(MoDTC)、ジチオリン酸モリブデン(以下、MoDTPともいう)及びモリブデン酸のアミン塩(以下、Moアミン塩ともいう)から選ばれる少なくとも一種が好適に用いられる。モリブデン系摩擦調整剤の中では、効果の点でMoDTCが好ましい。これらは、一種あるいは二種以上組み合わせて使用することができ、その好ましい配合量は、組成物全量に基づきモリブテン量として好ましくは10〜1000質量ppm、より好ましくは100〜800質量ppmの範囲である。モリブデン量が10質量ppm未満では十分な低摩擦性が得られないし、1000重量ppmを超えるとその量の割には摩擦特性の向上効果がみられない。
MoDTCは下記一般式(I)で表される。
3. Friction modifier In addition, in the lubricating oil composition for an internal combustion engine of the present invention, it is preferable to blend a molybdenum friction modifier or an ashless friction modifier in order to improve fuel saving characteristics. More preferably, a molybdenum friction modifier and an ashless friction modifier are used in combination.
As the molybdenum friction modifier, at least one selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (hereinafter also referred to as MoDTP), and an amine salt of molybdic acid (hereinafter also referred to as Mo amine salt) is preferably used. . Among molybdenum-based friction modifiers, MoDTC is preferable in terms of effects. These can be used singly or in combination of two or more, and the preferred blending amount is preferably in the range of 10 to 1000 ppm by mass, more preferably 100 to 800 ppm by mass as the amount of molybdenum based on the total amount of the composition. . If the amount of molybdenum is less than 10 ppm by mass, sufficient low friction cannot be obtained, and if it exceeds 1000 ppm by weight, the effect of improving the friction characteristics is not seen for that amount.
MoDTC is represented by the following general formula (I).

Figure 2011195734
Figure 2011195734

一般式(I)において、R1〜R4は炭素数5〜16の炭化水素基であり、全て同一でも異なっていてもよい。XはS(硫黄原子)又はO(酸素原子)である。R1〜R4で表される炭化水素基としては、例えば、炭素数5〜16のアルキル基、炭素数5〜16のアルケニル基、炭素数5〜16のシクロアルキル基、炭素数5〜16のアルキルアリール基、炭素数5〜16のアリールアルキル基などを挙げることができる。炭素数5〜16の炭化水素の具体例としては、各種ペンチル基,各種ヘキシル基,各種ヘプチル基,各種オクチル基,各種ノニル基,各種デシル基,各種ウンデシル基,各種ドデシル基,各種トリデシル基,各種テトラデシル基,各種ペンタデシル基,各種ヘキサデシル基,各種オクテニル基,各種ノネニル基,各種デセニル基,各種ウンデセニル基,各種ドデセニル基,各種トリデセニル基,各種テトラデセニル基,各種ペンタデセニル基,シクロヘキシル基,ジメチルシクロヘキシル基,エチルシクロヘキシル基,メチルシクロヘキシルメチル基,シクロヘキシルエチル基,プロピルシクロヘキシル基,ブチルシクロヘキシル基,ヘプチルシクロヘキシル基,フェニル基,トリル基,ジメチルフェニル基,ブチルフェニル基,ノニルフェニル基,メチルベンジル基,フェニルエチル基,ナフチル基,ジメチルナフチル基などを挙げることができる。
また、MoDTPは下記一般式(II)で表される。
In general formula (I), R < 1 > -R < 4 > is a C5-C16 hydrocarbon group, and may be the same or different altogether. X is S (sulfur atom) or O (oxygen atom). Examples of the hydrocarbon group represented by R 1 to R 4 include an alkyl group having 5 to 16 carbon atoms, an alkenyl group having 5 to 16 carbon atoms, a cycloalkyl group having 5 to 16 carbon atoms, and 5 to 16 carbon atoms. And an arylalkyl group having 5 to 16 carbon atoms. Specific examples of the hydrocarbon having 5 to 16 carbon atoms include various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, Various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, cyclohexyl groups, dimethylcyclohexyl groups , Ethylcyclohexyl group, methylcyclohexylmethyl group, cyclohexylethyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclohexyl group, phenyl group, tolyl group, dimethylphenyl group, butylphenyl group, nonylphenol Group, can be exemplified a methyl benzyl group, phenylethyl group, a naphthyl group, dimethyl naphthyl group and the like.
MoDTP is represented by the following general formula (II).

Figure 2011195734
Figure 2011195734

一般式(II)において、R5〜R8は炭素数5〜16の炭化水素基であり、全て同一でも異なっていてもよい。YはS(硫黄原子)又はO(酸素原子)である。R5〜R8で表される炭化水素基としては、例えば、炭素数5〜16のアルキル基、炭素数5〜16のアルケニル基、炭素数5〜16のシクロアルキル基、炭素数5〜16のアルキルアリール基、炭素数5〜16のアリールアルキル基などを挙げることができる。炭素数5〜16の炭化水素の具体例としては、各種ペンチル基,各種ヘキシル基,各種ヘプチル基,各種オクチル基,各種ノニル基,各種デシル基,各種ウンデシル基,各種ドデシル基,各種トリデシル基,各種テトラデシル基,各種ペンタデシル基,各種ヘキサデシル基,各種オクテニル基,各種ノネニル基,各種デセニル基,各種ウンデセニル基,各種ドデセニル基,各種トリデセニル基,各種テトラデセニル基,各種ペンタデセニル基,シクロヘキシル基,ジメチルシクロヘキシル基,エチルシクロヘキシル基,メチルシクロヘキシルメチル基,シクロヘキシルエチル基,プロピルシクロヘキシル基,ブチルシクロヘキシル基,ヘプチルシクロヘキシル基,フェニル基,トリル基,ジメチルフェニル基,ブチルフェニル基,ノニルフェニル基,メチルベンジル基,フェニルエチル基,ナフチル基,ジメチルナフチル基などを挙げることができる。
Moアミン塩は下記一般式(III)で表されるモリブデン酸の第二級アミン塩である。
In general formula (II), R < 5 > -R < 8 > is a C5-C16 hydrocarbon group, and may be same or different altogether. Y is S (sulfur atom) or O (oxygen atom). Examples of the hydrocarbon group represented by R 5 to R 8, for example, an alkyl group having 5 to 16 carbon atoms, an alkenyl group having 5 to 16 carbon atoms, a cycloalkyl group having 5 to 16 carbon atoms, carbon atoms 5-16 And an arylalkyl group having 5 to 16 carbon atoms. Specific examples of the hydrocarbon having 5 to 16 carbon atoms include various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, Various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, cyclohexyl groups, dimethylcyclohexyl groups , Ethylcyclohexyl group, methylcyclohexylmethyl group, cyclohexylethyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclohexyl group, phenyl group, tolyl group, dimethylphenyl group, butylphenyl group, nonylphenol Group, can be exemplified a methyl benzyl group, phenylethyl group, a naphthyl group, dimethyl naphthyl group and the like.
The Mo amine salt is a secondary amine salt of molybdic acid represented by the following general formula (III).

Figure 2011195734
Figure 2011195734

一般式(III)において、Rは炭素数5〜18の炭化水素基であり、4個の炭化水素基は同一でも、異なっていてもよい。炭素数5〜18の炭化水素基としては、例えば、炭素数5〜18のアルキル基、炭素数5〜18のアルケニル基、炭素数5〜18のシクロアルキル基、炭素数5〜18のアルキルアリール基、炭素数5〜18のアリールアルキル基などを挙げることができる。炭素数5〜18の炭化水素の具体例としては、各種ペンチル基,各種ヘキシル基,各種ヘプチル基,各種オクチル基,各種ノニル基,各種デシル基,各種ウンデシル基,各種ドデシル基,各種トリデシル基,各種テトラデシル基,各種ペンタデシル基,各種ヘキサデシル基,各種ヘプタデシル基,各種オクタデシル基,各種オクテニル基,各種ノネニル基,各種デセニル基,各種ウンデセニル基,各種ドデセニル基,各種トリデセニル基,各種テトラデセニル基,各種ペンタデセニル基,シクロヘキシル基,ジメチルシクロヘキシル基,エチルシクロヘキシル基,メチルシクロヘキシルメチル基,シクロヘキシルエチル基,プロピルシクロヘキシル基,ブチルシクロヘキシル基,ヘプチルシクロヘキシル基,フェニル基,トリル基,ジメチルフェニル基,ブチルフェニル基,ノニルフェニル基,メチルベンジル基,フェニルエチル基,ナフチル基,ジメチルナフチル基などを挙げることができる。   In the general formula (III), R is a hydrocarbon group having 5 to 18 carbon atoms, and the four hydrocarbon groups may be the same or different. Examples of the hydrocarbon group having 5 to 18 carbon atoms include an alkyl group having 5 to 18 carbon atoms, an alkenyl group having 5 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, and an alkylaryl having 5 to 18 carbon atoms. And arylalkyl groups having 5 to 18 carbon atoms. Specific examples of the hydrocarbon having 5 to 18 carbon atoms include various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, Various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups Group, cyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, methylcyclohexylmethyl group, cyclohexylethyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclohexyl group, phenyl group, tolyl group, dimethyl group Eniru group, butylphenyl group, nonylphenyl group, a methyl benzyl group, phenylethyl group, a naphthyl group, dimethyl naphthyl group and the like.

無灰系摩擦調整剤としては、例えば、脂肪酸、高級アルコール、脂肪酸エステル、油脂類、アミン、アミド、硫化エステル等が挙げられる。これらの摩擦調整剤は、単独で又は複数種を任意に組み合わせて含有させることができるが、通常、その配合量は、組成物全量基準で0.01〜10質量%の範囲である。   Examples of the ashless friction modifier include fatty acids, higher alcohols, fatty acid esters, fats and oils, amines, amides, and sulfurized esters. These friction modifiers can be contained alone or in any combination of a plurality of types, but the compounding amount is usually in the range of 0.01 to 10% by mass based on the total amount of the composition.

4.内燃機関用潤滑油組成物
本発明の内燃機関用潤滑油組成物は、基油の粘度指数、Noack蒸発量(250℃×1h)、オレフィン重合体、高分子化合物の質量平均分子量及び高分子化合物の配合量を上記規定範囲とすることで得ることができる。このような配合であれば、粘度指数が135若しくは140以上で、騒音が低く、ギヤピッチングなどの疲労損傷を抑制する効果に優れた省燃費型内燃機関用潤滑油組成物が得られる。
4). Lubricating oil composition for internal combustion engine The lubricating oil composition for internal combustion engine of the present invention comprises a viscosity index of base oil, Noack evaporation (250 ° C. × 1 h), olefin polymer, mass average molecular weight of polymer compound and polymer compound It can obtain by making the compounding quantity of the above-mentioned specified range. Such a blend provides a fuel-saving internal combustion engine lubricating oil composition having a viscosity index of 135 or 140, low noise, and excellent effects of suppressing fatigue damage such as gear pitching.

また、本組成物は、150℃における高せん断時の粘度低下率が、低せん断時の粘度に対して3.0%以下であることが好ましい。高せん断時の粘度低下率が3.0%を超える内燃機関用潤滑油は、粘度低下を見越して低せん断粘度を高く設定する必要があり、省燃費性を悪化させてしまうからである。
さらに、潤滑油組成物は、100℃における動粘度が11.0mm2/s未満であることが好ましい。11.0mm2/s以上になると、内燃機関用潤滑油の実使用温度領域(80℃〜100℃)の動粘度としては高いため、省燃費化を図ることができないからである。
特に、潤滑油組成物は、150℃における高せん断粘度がSAE粘度グレードで30相当の2.9mPa・s以上の場合、100℃おける動粘度が、9.0mm2/s未満であることが望ましく、150℃における高せん断粘度がSAE粘度グレードで20相当の2.6mPa・s以上の場合は、100℃おける動粘度が、7.5mm2/s未満が望ましい。これらの100℃動粘度を超えると、実使用温度領域(80℃〜100℃)における内燃機関用潤滑油の粘性が高くなり過ぎてしまい、従来油と比較して省燃費化を図ることができないからである。
Moreover, it is preferable that this composition is 3.0% or less with respect to the viscosity at the time of low shear in the viscosity decreasing rate at the time of high shear at 150 degreeC. This is because a lubricating oil for internal combustion engines having a viscosity reduction rate of more than 3.0% during high shear needs to set a high low shear viscosity in anticipation of the viscosity reduction and deteriorates fuel economy.
Furthermore, the lubricating oil composition preferably has a kinematic viscosity at 100 ° C. of less than 11.0 mm 2 / s. This is because if it is 11.0 mm 2 / s or more, the kinematic viscosity in the actual operating temperature range (80 ° C. to 100 ° C.) of the lubricating oil for internal combustion engines is high, so that it is not possible to save fuel.
In particular, the lubricating oil composition preferably has a kinematic viscosity at 100 ° C. of less than 9.0 mm 2 / s when the high shear viscosity at 150 ° C. is 2.9 mPa · s or more equivalent to 30 in the SAE viscosity grade. When the high shear viscosity at 150 ° C. is 2.6 mPa · s or more corresponding to 20 in the SAE viscosity grade, the kinematic viscosity at 100 ° C. is preferably less than 7.5 mm 2 / s. If these 100 ° C. kinematic viscosities are exceeded, the viscosity of the lubricating oil for internal combustion engines in the actual operating temperature range (80 ° C. to 100 ° C.) becomes too high, and it is not possible to save fuel consumption compared to conventional oils. Because.

5.その他の添加剤
さらに、本発明の内燃機関用潤滑油組成物においては、本発明の目的が損なわれない範囲で、無灰系分散剤、金属系清浄剤、極圧剤、金属不活性化剤、防錆剤、消泡剤、抗乳化剤及び着色剤等に代表される各種添加剤を単独で、又は数種組み合わせて配合してもよい。
無灰系分散剤としては、質量平均分子量が900〜3,500のポリブテニル基を有するポリブテニルコハク酸イミド、ポリブテニルベンジルアミン、ポリブテニルアミン、及びこれらのホウ酸変性物等の誘導体等が挙げられる。これらの無灰分散剤は、単独で又は複数種を任意に組み合わせて含有させることができるが、通常その配合量は、組成物全量基準で0.01〜10質量%の範囲である。
5. Other Additives Furthermore, in the lubricating oil composition for internal combustion engines of the present invention, an ashless dispersant, a metallic detergent, an extreme pressure agent, and a metal deactivator within a range that does not impair the object of the present invention. Various additives typified by rust preventives, antifoaming agents, demulsifiers and colorants may be used alone or in combination.
Ashless dispersants include polybutenyl succinimide having a polybutenyl group having a weight average molecular weight of 900 to 3,500, polybutenylbenzylamine, polybutenylamine, and derivatives thereof such as boric acid-modified products Etc. These ashless dispersants can be contained alone or in any combination of two or more kinds, but the compounding amount is usually in the range of 0.01 to 10% by mass based on the total amount of the composition.

金属系清浄剤としては、例えば、アルカリ金属(ナトリウム(Na)、カリウム(K)等)又はアルカリ土類金属(カルシウム(Ca)、マグネシウム(Mg)等)のスルフォネート、フェネート、サリシレート及びナフテネート等が挙げられる。これらは単独で又は複数種を組み合わせて使用できる。これらの金属系清浄剤の全塩基価及び配合量は、要求される潤滑油の性能に応じて適宜選択すればよい。全塩基価は、過塩素酸法で通常0〜500mgKOH/g、望ましくは10〜400mgKOH/gである。また、その配合量は、通常、組成物全量基準で0.1〜10質量%の範囲である。   Examples of metal detergents include sulfonates, phenates, salicylates, and naphthenates of alkali metals (sodium (Na), potassium (K), etc.) or alkaline earth metals (calcium (Ca), magnesium (Mg), etc.). Can be mentioned. These can be used alone or in combination. What is necessary is just to select suitably the total base number and compounding quantity of these metal type detergents according to the performance of the required lubricating oil. The total base number is usually from 0 to 500 mgKOH / g, desirably from 10 to 400 mgKOH / g by the perchloric acid method. Moreover, the compounding quantity is the range of 0.1-10 mass% normally on the composition whole quantity basis.

極圧剤としては、例えば、硫化オレフィン、ジアルキルポリスルフィド、ジアリールアルキルポリスルフィド、ジアリールポリスルフィドなどの硫黄系化合物、リン酸エステル、チオリン酸エステル、亜リン酸エステル、アルキルハイドロゲンホスファイト、リン酸エステルアミン塩、亜リン酸エステルアミン塩などのリン系化合物等が挙げられ、通常、その配合量は、組成物全量基準で0.01〜10質量%の範囲である。   Examples of extreme pressure agents include sulfur compounds such as sulfurized olefins, dialkyl polysulfides, diarylalkyl polysulfides, diaryl polysulfides, phosphate esters, thiophosphate esters, phosphite esters, alkyl hydrogen phosphites, phosphate ester amine salts, Examples thereof include phosphorus compounds such as phosphite amine salts, and the compounding amount is usually in the range of 0.01 to 10% by mass based on the total amount of the composition.

金属不活性化剤としては、ベンゾトリアゾール、トリアゾール誘導体、ベンゾトリアゾール誘導体、チアジアゾール誘導体等が挙げられ、通常、その配合量は、組成物全量基準で0.01〜3質量%の範囲である。
防錆剤としては、例えば、脂肪酸、アルケニルコハク酸ハーフエステル、脂肪酸セッケン、アルキルスルホン酸塩、アルカリ土類金属(カルシウム(Ca)、マグネシウム(Mg)、バリウム(Ba)等)のスルフォネート、フェネート、サリシレート及びナフテネート、多価アルコール脂肪酸エステル、脂肪酸アミン、酸化パラフィン、アルキルポリオキシエチレンエーテル等が挙げられ、通常、その配合量は、組成物全量基準で0.01〜5質量%の範囲である。
消泡剤としては、液状シリコーンが適しており、例えば、メチルシリコーン、フルオロシリコーン、及びポリアクリレート等が使用可能である。これら消泡剤の好ましい配合量は、組成物全量基準で0.0005〜0.1質量%である。
抗乳化剤として、エチレンプロピレンブロックポリマー、アルカリ土類金属(カルシウム(Ca)、マグネシウム(Mg)等)のスルフォネート、フェネート、サリシレート及びナフテネートなどを用いることができ、通常その配合量は0.0005〜1質量%である。
着色剤としては、染料や顔料等を用いることができ、通常、その配合量は、組成物全量基準で0.001〜1質量%である。
Examples of the metal deactivator include benzotriazole, triazole derivatives, benzotriazole derivatives, thiadiazole derivatives, and the like. Usually, the blending amount is in the range of 0.01 to 3% by mass based on the total amount of the composition.
Examples of the rust inhibitor include sulfonates, phenates of fatty acids, alkenyl succinic acid half esters, fatty acid soaps, alkyl sulfonates, alkaline earth metals (calcium (Ca), magnesium (Mg), barium (Ba), etc.), Salicylates and naphthenates, polyhydric alcohol fatty acid esters, fatty acid amines, oxidized paraffins, alkyl polyoxyethylene ethers and the like can be mentioned, and the compounding amount is usually in the range of 0.01 to 5% by mass based on the total amount of the composition.
As the antifoaming agent, liquid silicone is suitable, and for example, methyl silicone, fluorosilicone, polyacrylate, and the like can be used. A preferable blending amount of these antifoaming agents is 0.0005 to 0.1% by mass based on the total amount of the composition.
As demulsifiers, ethylene propylene block polymers, sulfonates of alkaline earth metals (calcium (Ca), magnesium (Mg), etc.), phenates, salicylates, naphthenates, etc. can be used. % By mass.
As the colorant, dyes, pigments, and the like can be used. Usually, the blending amount is 0.001 to 1% by mass based on the total amount of the composition.

このようにして調製された本発明の内燃機関用潤滑油組成物は、上述のように配合してなるので、低粘度であるが、蒸発減量が少なく、粘度指数が高く、かつ、高温高せん断時における粘度低下率が低いという効果を有する。特に、そのような性質を有するとともに、騒音を低減する効果、疲労損傷を抑制する効果及び省燃費性を有する。それ故、内燃機関用潤滑油、特に二輪車用4サイクルエンジン用潤滑油として有用な内燃機関用潤滑油組成物として好適に用いることができる。   The lubricating oil composition for an internal combustion engine of the present invention thus prepared is blended as described above, so it has a low viscosity but a low evaporation loss, a high viscosity index, and a high temperature and high shear. It has the effect that the viscosity reduction rate at the time is low. In particular, in addition to having such properties, it has an effect of reducing noise, an effect of suppressing fatigue damage, and fuel efficiency. Therefore, it can be suitably used as a lubricating oil composition for an internal combustion engine that is useful as a lubricating oil for an internal combustion engine, particularly a four-cycle engine lubricating oil for a motorcycle.

次に、本発明を実施例によりさらに詳しく説明するが、本発明は、以下の実施例によってなんら限定されるものでない。
なお、各例における潤滑油組成物(試料油)の性状は以下のような方法で求めた。
(1)動粘度(40℃、100℃)及び粘度指数
JIS K 2283の方法により測定した。
(2)HTHS粘度(150℃)
ASTM D4683の方法により、TBS高温粘度計(Tapered Bearing Simulator)を用いて測定した。試験条件を以下に示す。
・せん断速度 :106sec-1
・回転数(モーター) :3000rpm
・間隔(ローター/ステーター):2〜3μm
・試料量 :20〜50ml
・測定時間 :校正4〜6時間
:試験15分間
(3)低温粘度(CCS粘度)
JIS K2606に準拠し、−25℃、−30℃における粘度を測定した。
(4)Noack蒸発量
CEC−L−40−A−93、ASTM D5800/Aに規定される方法で蒸発量を測定した。試験条件は、250℃で1時間である。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by the following examples.
The properties of the lubricating oil composition (sample oil) in each example were determined by the following method.
(1) Kinematic viscosity (40 ° C., 100 ° C.) and viscosity index It was measured by the method of JIS K 2283.
(2) HTHS viscosity (150 ° C)
It was measured by the method of ASTM D4683 using a TBS high temperature viscometer (Tapered Bearing Simulator). Test conditions are shown below.
・ Shear rate: 10 6 sec -1
・ Rotation speed (motor): 3000rpm
・ Spacing (rotor / stator): 2 to 3 μm
-Sample volume: 20-50ml
・ Measurement time: Calibration 4-6 hours
: Test 15 minutes (3) Low temperature viscosity (CCS viscosity)
Based on JIS K2606, the viscosity at -25 ° C and -30 ° C was measured.
(4) Noack evaporation amount The evaporation amount was measured by the method prescribed in CEC-L-40-A-93 and ASTM D5800 / A. The test conditions are 1 hour at 250 ° C.

(5)騒音性評価
下記のエンジンモータリング装置と運転条件下で発生する音を、下記の方法によって騒音測定を行った。
[エンジンモータリング装置と運転条件]
エンジン:二輪車用水冷600CC、4気筒エンジン
駆動モーター:7.5kw
動弁形式:DOHC(直打)
エンジン回転数:3000rpm
オイルパン油温:100℃
[騒音測定方法]
騒音計(小野測器社製 LA5560)を用い、周波数分析装置(小野測器製Repolyzer XN−8100)にて、6300Hzの周波数のパワースペクトル(dB)を測定した。
(6)省燃費性の評価
以下のような仕様のエンジンにエンジン油を充填してモータリングトルク試験を行い、所定回転数におけるトルク(dB)を測定した。試験条件を以下に示す。
・エンジンモータリング装置と運転条件
・エンジン:二輪車用水冷600CC 4気筒エンジン
・動弁形式:DOHC(直打)
・エンジン回転数:5000rpm
・オイルパン油温:100℃
・駆動モーター:7.5kw
(7)疲労寿命
4球転動疲労試験機を用い、下記の要領にて疲労寿命を測定した。
(ベアリング)
材質 :ベアリング鋼
試験片 :Φ60×暑さ5mm
試験鋼球寸法:φ3/8 インチ
(試験条件)
荷重:147N
回転速度:2200rpm
油温:120℃
(評価方法)
試験片にフレーキングが発生するまでの時間を疲労寿命とし、6回の試験の結果をワイブル統計処理し、L50(分)を算出した。
(8)粘度低下率
100℃における動粘度と粘度指数から、150℃における動粘度を求めた値に、JIS K 2249に準じて測定した15℃における密度と80℃における密度から、150℃における密度を外挿して求めた値を掛け合わせることで、150℃における低せん断時の粘度とした。この値と上記HTHS粘度(150℃)より、粘度低下率を算出した。
(5) Noise evaluation The noise generated under the following engine motoring device and operating conditions was measured by the following method.
[Engine motoring device and operating conditions]
Engine: Water-cooled 600CC for motorcycles, 4-cylinder engine Drive motor: 7.5kw
Valve type: DOHC (Direct stroke)
Engine speed: 3000rpm
Oil pan oil temperature: 100 ° C
[Noise measurement method]
Using a sound level meter (LA5560 manufactured by Ono Sokki Co., Ltd.), a power spectrum (dB) having a frequency of 6300 Hz was measured with a frequency analyzer (Repolizer XN-8100 manufactured by Ono Sokki).
(6) Evaluation of fuel efficiency The engine with the following specifications was filled with engine oil and a motoring torque test was performed to measure the torque (dB) at a predetermined rotational speed. Test conditions are shown below.
・ Engine motoring device and operating conditions ・ Engine: Water-cooled 600CC 4-cylinder engine for motorcycles ・ Valve type: DOHC
・ Engine speed: 5000rpm
・ Oil pan oil temperature: 100 ℃
・ Drive motor: 7.5kw
(7) Fatigue life Fatigue life was measured in the following manner using a four-ball rolling fatigue tester.
(bearing)
Material: Bearing steel Test piece: Φ60 x Heat 5mm
Test steel ball dimensions: φ3 / 8 inch (Test conditions)
Load: 147N
Rotational speed: 2200 rpm
Oil temperature: 120 ° C
(Evaluation methods)
The time until flaking occurred on the test piece was defined as the fatigue life, the results of six tests were subjected to Weibull statistical processing, and L50 (minutes) was calculated.
(8) Viscosity reduction rate From the kinematic viscosity at 100 ° C. and the viscosity index, to the value obtained from kinematic viscosity at 150 ° C. From the density at 15 ° C. and the density at 80 ° C. measured according to JIS K 2249, the density at 150 ° C. Was multiplied by the value obtained by extrapolating to obtain a viscosity at 150 ° C. at low shear. From this value and the HTHS viscosity (150 ° C.), the viscosity reduction rate was calculated.

〔実施例1〜5、比較例1〜7〕
以下に示す各種基油、各種共重合体、高分子化合物、添加剤を用いて、第1表の組成にしたがって内燃機関用潤滑油組成物(試料油)を調製した。
調製した試料油は前記した方法で各性状を評価し、結果を第1表に示す。
(基油)
・基油−1 鉱物油系水素化分解基油(API分類GIII)100N、100℃動粘度4.175mm2/s、粘度指数131、硫黄分0.01質量%以下、%CA0、Noack蒸発量14質量%
・基油−2 鉱物油系水素化分解基油(API分類GIII)、150N、100℃動粘度6.274mm2/s、粘度指数129、硫黄分0.01質量%以下、%CA0、Noack蒸発量6質量%
・基油−3 鉱物油系水素化精製基油(API分類GII)、150N、100℃動粘度5.284mm2/s、粘度指数104、硫黄分0.01質量%以下、%CA0、Noack蒸発量14質量%
・基油−4 鉱物油系水素化精製基油(API分類GII)、500N、100℃動粘度10.89mm2/s、粘度指数107、硫黄分0.01質量%以下、%CA0、Noack蒸発量4質量%
・基油−5 鉱物油系水素化精製基油(API分類GII)、ブライトストック、API分類GII)、100℃動粘度30.86mm2/s、粘度指数107、硫黄分0.01質量%以下、%CA0、Noack蒸発量2質量%以下
[Examples 1-5, Comparative Examples 1-7]
A lubricating oil composition (sample oil) for an internal combustion engine was prepared according to the composition shown in Table 1 using various base oils, various copolymers, polymer compounds, and additives shown below.
The prepared sample oil was evaluated for each property by the method described above, and the results are shown in Table 1.
(Base oil)
・ Base oil-1 Mineral oil hydrocracked base oil (API classification GIII) 100N, 100 ° C. Kinematic viscosity 4.175 mm 2 / s, Viscosity index 131, Sulfur content 0.01 mass% or less,% C A 0, Noack Evaporation 14% by mass
Base oil-2 Mineral oil hydrocracked base oil (API classification GIII), 150 N, 100 ° C. kinematic viscosity 6.274 mm 2 / s, viscosity index 129, sulfur content 0.01 mass% or less,% C A 0, Noack evaporation 6 mass%
Base oil-3 Mineral oil hydrorefined base oil (API classification GII), 150 N, 100 ° C. kinematic viscosity 5.284 mm 2 / s, viscosity index 104, sulfur content 0.01 mass% or less,% C A 0, Noack evaporation 14% by mass
Base oil-4 Mineral oil hydrorefined base oil (API classification GII), 500 N, 100 ° C. kinematic viscosity 10.89 mm 2 / s, viscosity index 107, sulfur content 0.01 mass% or less,% C A 0, Noack evaporation 4% by mass
Base oil-5 Mineral oil hydrorefined base oil (API classification GII), Brightstock, API classification GII), 100 ° C. kinematic viscosity 30.86 mm 2 / s, viscosity index 107, sulfur content 0.01 mass% or less ,% C A 0, Noack evaporation 2 mass% or less

(オレフィン重合体)
・共重合体−1 エチレン−α−オレフィン共重合体 質量平均分子量4,700 (三井化学社製 ルーカントHC600)
・共重合体−2 エチレン−α−オレフィン共重合体 質量平均分子量7,000 (三井化学社製 ルーカントHC2000)
(高分子化合物)
・高分子化合物―1 ポリメタクリレート(PMA)、 質量平均分子量45,000 (三洋化成工業社製 アクルーブC−728)
・高分子化合物―2 オレフィンコポリマー(OCP)、質量平均分子量100,000 (シェブロン社製 Paratone8057)
(流動点降下剤)
PMA、質量平均分子量690,000、(デグサ社製 PLEXOL−162)
(摩擦調整剤)
モリブデン系摩擦調整剤:モリブデン系摩擦調整剤としてモリブデンジアルキルジチオカルバメートを用いた。なお、モリブデン量としては4.5wt%である。
(DI剤)
パッケージ添加剤、ZnDTP(1.1)、金属系清浄剤(4)、硼素変性コハク酸イミドA(1)、硼素変性コハク酸イミドB(1)、ポリブテニルコハク酸イミド(2.1)、アミン系酸化防止剤(0.8)及び希釈油(残部)の混合物。( )内は質量%を示す。
(Olefin polymer)
-Copolymer-1 Ethylene-α-olefin copolymer Mass average molecular weight 4,700 (Lucant HC600 manufactured by Mitsui Chemicals)
-Copolymer-2 Ethylene-α-olefin copolymer Mass average molecular weight 7,000 (Mitsui Chemicals, Lucant HC2000)
(Polymer compound)
-High molecular compound-1 polymethacrylate (PMA), mass average molecular weight 45,000 (manufactured by Sanyo Chemical Industries, Inc. C-728)
-High molecular compound-2 olefin copolymer (OCP), mass average molecular weight 100,000 (Paratone 8057, manufactured by Chevron)
(Pour point depressant)
PMA, mass average molecular weight 690,000, (PLEXOL-162 manufactured by Degussa)
(Friction modifier)
Molybdenum friction modifier: Molybdenum dialkyldithiocarbamate was used as the molybdenum friction modifier. The molybdenum content is 4.5 wt%.
(DI agent)
Package additive, ZnDTP (1.1), metallic detergent (4), boron-modified succinimide A (1), boron-modified succinimide B (1), polybutenyl succinimide (2.1) , A mixture of amine antioxidant (0.8) and diluent oil (remainder). Figures in parentheses indicate mass%.

Figure 2011195734
Figure 2011195734

Figure 2011195734
Figure 2011195734

第1表の結果から以下のことが分かる。
(1)本発明の内燃機関用潤滑油組成物は、いずれも良好な低騒音性、耐疲労寿命性、省燃費性、耐蒸発性、及び、低粘度低下性を有する(実施例1〜5)。これに対し、本発明のいずれかの要件を満たさない組成物は、これらの性能のうちの一以上の性能を満たさない。
(2)具体的には、次のことが明確である。
(i)実施例1、実施例2及び実施例5の組成物は、粘度グレードが、5W−20油であるが、粘度グレードが10W−30で、より高粘度(動粘度)の比較例3の組成物と同等もしくはそれ以上に良好な低騒音性、耐疲労寿命性、耐蒸発性を有する。
(ii)実施例3の組成物は、粘度グレードが、10W−20油であるが、粘度グレードが40で、より粘度(動粘度)が高い比較例7の組成物と同等もしくはそれ以上に良好な低騒音性、耐疲労寿命性を有する。
(iii)実施例4の組成物は、粘度グレードが、10W−30油であるが、粘度グレードが10W−40で、より粘度(動粘度)が高い比較例4の組成物と同等もしくはそれ以上に良好な低騒音性、耐疲労寿命性、耐蒸発性を有する。
From the results in Table 1, the following can be understood.
(1) The lubricating oil composition for an internal combustion engine of the present invention has good low noise properties, fatigue life resistance, fuel economy, evaporation resistance, and low viscosity lowering properties (Examples 1 to 5). ). In contrast, compositions that do not meet any of the requirements of the present invention do not meet one or more of these capabilities.
(2) Specifically, the following is clear.
(I) The compositions of Example 1, Example 2 and Example 5 have a viscosity grade of 5W-20 oil, but the viscosity grade is 10W-30 and a higher viscosity (kinematic viscosity) Comparative Example 3 It has low noise properties, fatigue life resistance, and evaporation resistance that are equal to or better than the above composition.
(Ii) The composition of Example 3 has a viscosity grade of 10W-20 oil, but the viscosity grade is 40, which is equivalent to or better than the composition of Comparative Example 7 having a higher viscosity (kinematic viscosity). Low noise and fatigue life.
(Iii) The composition of Example 4 has a viscosity grade of 10W-30 oil, but the viscosity grade is 10W-40 and is equal to or higher than the composition of Comparative Example 4 having a higher viscosity (kinematic viscosity). Have good low noise, fatigue life and evaporation resistance.

本発明の内燃機関用潤滑油組成物は、低粘度であっても走行時の騒音を低減し、ギヤピッチングなどの疲労損傷を抑制し、オイル消費を低減し、かつ、良好な省燃費性を有する内燃機関用潤滑油組成物を提供することができる。したがって、二輪車用4サイクルエンジン用潤滑油にも効果的に使用できる内燃機関用潤滑油組成物として好適に利用できる。   The lubricating oil composition for an internal combustion engine of the present invention reduces running noise even when the viscosity is low, suppresses fatigue damage such as gear pitching, reduces oil consumption, and provides good fuel economy. The lubricating oil composition for internal combustion engines can be provided. Therefore, it can be suitably used as a lubricating oil composition for an internal combustion engine that can be effectively used as a lubricating oil for a four-cycle engine for a motorcycle.

Claims (5)

粘度指数が125以上であり、Noack蒸発量(250℃×1h)が15質量%以下である基油に、組成物全量を基準として、(A)質量平均分子量500以上10,000以下の炭素数2〜20のオレフィン重合体、及び/又は(B)質量平均分子量が10,000以上100,000未満の高分子化合物を0.1〜10質量%含み、(C)質量平均分子量100,000以上の高分子化合物の配合量が1.0質量%未満であることを特徴とする内燃機関用潤滑油組成物。   A base oil having a viscosity index of 125 or more and a Noack evaporation (250 ° C. × 1 h) of 15% by mass or less, based on the total amount of the composition, (A) a carbon number having a mass average molecular weight of 500 to 10,000 2 to 20 olefin polymers and / or (B) 0.1 to 10% by mass of a polymer compound having a mass average molecular weight of 10,000 or more and less than 100,000, and (C) a mass average molecular weight of 100,000 or more. A lubricating oil composition for internal combustion engines, wherein the amount of the polymer compound is less than 1.0% by mass. 前記高分子化合物が、ポリメタクリレート、オレフィン共重合体、スチレン共重合体、及びポリイソブチレンの中から選ばれる一種又は二種以上の高分子化合物である請求項1に記載の内燃機関用潤滑油組成物。   The lubricating oil composition for an internal combustion engine according to claim 1, wherein the polymer compound is one or two or more polymer compounds selected from polymethacrylate, olefin copolymer, styrene copolymer, and polyisobutylene. object. さらに、モリブデン系摩擦調整剤若しくは無灰系摩擦調整剤を配合したことを特徴とする請求項1又は2に記載の内燃機関用潤滑油組成物。   The lubricating oil composition for internal combustion engines according to claim 1 or 2, further comprising a molybdenum friction modifier or an ashless friction modifier. Noack蒸発量(250℃×1h)が10.0質量%以下であり、かつ、粘度指数が140以上である請求項1〜3のいずれかに記載の内燃機関用潤滑油組成物。   The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 3, wherein a Noack evaporation amount (250 ° C x 1h) is 10.0% by mass or less and a viscosity index is 140 or more. 二輪車用4サイクルエンジン用潤滑油である請求項1〜4のいずれかに記載の内燃機関用潤滑油組成物。   The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 4, which is a lubricating oil for a four-cycle engine for a motorcycle.
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