JP2004131742A - Lubricating oil composition - Google Patents
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本発明は、ディーゼルエンジンやガソリンエンジンあるいはジメチルエーテルを燃料とするエンジンやガスエンジンなどの内燃機関の潤滑に有用な潤滑油組成物に関する。さらに詳しくは、本発明は、低灰分含量、低リン含量、低硫黄含量、そして低塩素含量でありながらも高温清浄性に優れ、パティキュレートフィルタや、未燃焼の煤および燃料や潤滑油を酸化するために自動車に装着されている酸化触媒などの排ガス浄化装置への悪影響が少なく、近い将来における実施が予測される排ガス規制にも充分対応できる内燃機関用潤滑油組成物に関する。本発明は特に、走行用燃料として、硫黄含有量約０．０１重量％以下の炭化水素系燃料を用いる自動車、なかでも排ガス浄化装置（特にパティキュレートフィルタおよび酸化触媒）を備えたディーゼルエンジン搭載車において好適に用いられる、環境対応型の内燃機関用潤滑油組成物に関するものである。 The present invention relates to a lubricating oil composition useful for lubricating an internal combustion engine such as a diesel engine, a gasoline engine, an engine using dimethyl ether as a fuel, or a gas engine. More specifically, the present invention has a low ash content, a low phosphorus content, a low sulfur content, and a low chlorine content, yet has excellent high-temperature detergency, oxidizes particulate filters, unburned soot, fuel and lubricating oil. Therefore, the present invention relates to a lubricating oil composition for an internal combustion engine which has little adverse effect on an exhaust gas purifying device such as an oxidation catalyst mounted on an automobile and can sufficiently cope with exhaust gas regulations expected to be implemented in the near future. The present invention particularly relates to a vehicle using a hydrocarbon-based fuel having a sulfur content of about 0.01% by weight or less as a running fuel, and particularly a vehicle equipped with a diesel engine equipped with an exhaust gas purifying device (particularly, a particulate filter and an oxidation catalyst). The present invention relates to an environment-friendly lubricating oil composition for an internal combustion engine, which is suitably used in the above.
内燃機関、特にディーゼルエンジンに関し、パティキュレートおよびＮＯＸなどの排ガス成分による環境汚染に対する対策が重要な課題となっている。その対策としては、自動車へのパティキュレートフィルタ及び酸化触媒などの排ガス浄化装置の装着があるが、従来の内燃機関用潤滑油を用いた場合、パティキュレートフィルタに付着した煤は、排ガス浄化装置中で、酸化、燃焼により取り除かれるものの、燃焼により生成した金属酸化物や硫酸塩、カルボン酸塩などによるフィルタ閉塞の問題は解決されない。 Internal combustion engine, relates in particular diesel engines, measures against environmental pollution caused by exhaust gas components such as particulate and NO X is an important issue. As a countermeasure, an exhaust gas purifying device such as a particulate filter and an oxidation catalyst may be installed in an automobile. Thus, although removed by oxidation and combustion, the problem of filter blockage due to metal oxides, sulfates, carboxylate and the like generated by combustion cannot be solved.
一方、燃料中の硫黄分の存在は排ガス中への硫酸もしくは硫酸塩の混入につながり、特に酸化触媒への悪影響を考慮すると極力減らす必要があり、近い将来、燃料の低硫黄化は一段と進むものと考えられている。ディーゼルエンジン搭載自動車用の軽油を例にとれば、その含有硫黄分は、現在の硫黄分の約０．０５重量％から０．０１重量％以下、そしてさらには０．００１重量％前後まで減らされるものと予測されている。燃料の低硫黄化が進めば、硫酸等を中和するために必要とされた潤滑油中の金属系清浄剤（金属含有清浄剤）の添加量を低減することができる。一方、潤滑油の一部はエンジン中で潤滑に使用されると同時に、燃焼し、排ガスの一部と排出される。従って、潤滑油中の金属分、硫黄分もまたできるだけ低くする方が好ましいことは当然である。さらに、潤滑油中のリン分も減らすことが触媒の劣化対策のうえで好ましい。またダイオキシン類の発生の可能性を考慮すると、潤滑油中の塩素分も極力低減することが好ましい。 On the other hand, the presence of sulfur in the fuel leads to the incorporation of sulfuric acid or sulfate in the exhaust gas, and it is necessary to reduce it as much as possible, especially considering the adverse effect on oxidation catalysts. It is believed that. Taking diesel oil for diesel engine vehicles as an example, its sulfur content is reduced from about 0.05% by weight of the current sulfur content to less than 0.01% by weight, and further to around 0.001% by weight. Is expected. As the sulfur content of fuel decreases, the amount of metal-based detergent (metal-containing detergent) in lubricating oil required to neutralize sulfuric acid and the like can be reduced. On the other hand, a part of the lubricating oil is used for lubrication in the engine, and at the same time, burns and is discharged as a part of the exhaust gas. Therefore, it is natural that it is preferable to reduce the metal content and the sulfur content in the lubricating oil as much as possible. Further, it is preferable to reduce the phosphorus content in the lubricating oil in order to prevent the deterioration of the catalyst. In consideration of the possibility of generation of dioxins, it is preferable to reduce the chlorine content in the lubricating oil as much as possible.
従来、自動車、建設機械、発電機等で用いられるディーゼル内燃機関は、硫黄分が約０．０５重量％以上の燃料（軽油や重油）を用いて運転されることが一般的であって、ディーゼルエンジン用潤滑油としては、通常、硫酸灰分約１．３〜２重量％、硫黄分約０．３〜０．７重量％、リン分約０．１〜０．１３重量％、のものが多くの場合用いられてきた。また、塩素分も５０〜１００重量ｐｐｍ以上の潤滑油が一般的であった。 2. Description of the Related Art Conventionally, diesel internal combustion engines used in automobiles, construction machines, generators, and the like are generally operated using a fuel (light oil or heavy oil) having a sulfur content of about 0.05% by weight or more. Most lubricating oils for engines generally have a sulfated ash content of about 1.3 to 2% by weight, a sulfur content of about 0.3 to 0.7% by weight, and a phosphorus content of about 0.1 to 0.13% by weight. Has been used in the case of Lubricating oils having a chlorine content of 50 to 100 ppm by weight or more were generally used.
特許文献１には、前記したような低硫黄含有量の燃料を用いたディーゼルエンジンの潤滑に適した潤滑油組成物として、（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェノール）カルボン酸アルキルエステル、コハク酸イミド型無灰性分散剤、そしてアミン系またはフェノール系の無灰系酸化防止剤をそれぞれ特定量含有する無灰型潤滑油組成物が記載されている。
特許文献２には、特定の無灰系分散剤、油溶性酸化防止剤、そして油溶性ジヒドロカルビルジチオフォスフォレートとを含む、全硫酸灰分量が少ない重質ディーゼルエンジン用潤滑油組成物が記載されている。
特許文献３には、高温清浄性に優れ、パティキュレートトラップや酸化触媒への悪影響が少なく、将来の排気ガス規制に対応できる潤滑油組成物として、基油に対してホウ素含有無灰性分散剤とジチオリン酸亜鉛、そして場合により、無灰性酸化防止剤を配合した潤滑油組成物であって、ホウ素含有量が０．１重量％以上、ホウ素／リン含有量被が０．８以上、そして全重酸灰分量が１．０重量％以下の潤滑油組成物が記載されている。
Patent Document 2 discloses a lubricating oil composition for a heavy-duty diesel engine having a small amount of total sulfated ash, comprising a specific ashless dispersant, an oil-soluble antioxidant, and an oil-soluble dihydrocarbyl dithiophosphorate. Have been.
Patent Literature 3 discloses a boron-containing ashless dispersant based on a base oil as a lubricating oil composition having excellent high-temperature detergency, little adverse effect on particulate traps and oxidation catalysts, and capable of meeting future exhaust gas regulations. And a zinc dithiophosphate, and optionally, an ashless antioxidant, wherein the lubricating oil composition has a boron content of 0.1% by weight or more, a boron / phosphorus content of 0.8 or more, and A lubricating oil composition having a total heavy acid ash content of 1.0% by weight or less is described.
本発明は、従来用いられている潤滑油組成物に比べて、低灰分含量、低リン含量、低硫黄含量かつ低塩素含量であって、パティキュレートフィルタや酸化触媒などの排ガス浄化装置への悪影響が低減され、一方では、従来用いられている潤滑油組成物と同等もしくはそれ以上の高温清浄性を示し、将来の排ガス規制に充分対応でき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。 The present invention has a low ash content, a low phosphorus content, a low sulfur content, and a low chlorine content as compared with conventionally used lubricating oil compositions, and has an adverse effect on exhaust gas purification devices such as particulate filters and oxidation catalysts. On the other hand, an object of the present invention is to provide a lubricating oil composition for an internal combustion engine which exhibits high-temperature detergency equivalent to or higher than that of a conventionally used lubricating oil composition and can sufficiently cope with future exhaust gas regulations. I do.
潤滑油組成物を研究する研究者や技術者にとって、一般的に知られていることであるが、内燃機関用潤滑油組成物の単なる低灰分化、低リン化、かつ低硫黄化は、従来の潤滑油組成物に一般的に用いられいる金属系清浄剤およびジチオリン酸亜鉛の添加量の削減を意味し、高温清浄性や酸化安定性の低下につながる。 As is generally known to researchers and engineers studying lubricating oil compositions, mere low ash differentiation, low phosphorus, and low sulfur of lubricating oil compositions for internal combustion engines are conventionally known. This means a reduction in the amount of the metal-based detergent and zinc dithiophosphate generally used in the lubricating oil composition described above, which leads to a decrease in high-temperature detergency and oxidation stability.
本発明者は鋭意研究を重ねた結果、低灰分化、低リン化、かつ低硫黄化を行ないながらも、潤滑油組成物中に、特定の無灰系酸化防止剤を添加し、さらに金属系清浄剤（金属成分含有清浄剤）に含まれる有機酸金属塩（いわゆる石鹸成分もしくはソープ成分）を特定範囲の量にて存在させることにより、高温清浄性や酸化安定性を高いレベルに維持することを可能にする潤滑油組成物の配合を見出した。本発明は、この新規な知見に基づき完成されたものである。
従って、本発明は、鉱油および／または合成油からなる硫黄含有量０．１重量％以下（好ましくは０．０３重量％以下）の基油に少なくとも、組成物の全重量に基づき、
ａ）アルケニルもしくはアルキルこはく酸イミドあるいはその誘導体である無灰性分散剤が窒素含有量換算値で０．０１〜０．３重量％、
ｂ）硫黄含有量が３％以下で全塩基価１０〜３５０ｍｇＫＯＨ／ｇの金属含有清浄剤（いわゆる金属系清浄剤）が硫酸灰分換算値で０．１〜１重量％、
ｃ）ジアルキルジチオリン酸亜鉛が、リン含有量換算値で０．０１〜０．１重量％、そして
ｄ）酸化防止性のフェノール化合物および／または酸化防止性のアミン化合物が０．０１〜５重量％、
の量にて溶解もしくは分散されていて、組成物の全重量に基づき、硫酸灰分量が０．１〜１重量％の範囲、リン含有量が０．０１〜０．１重量％の範囲、そして硫黄含有量が０．０１〜０．３重量％の範囲にあって、塩素含有量が４０ｐｐｍ以下であり、さらに金属含有清浄剤に含まれる有機酸金属塩が組成物中に０．２〜７重量％（好ましくは０．５〜５重量％、さらに好ましくは１．０〜３重量％）存在することを特徴とする潤滑油組成物にある。
As a result of intensive studies, the present inventors have conducted low ash differentiation, low phosphorus, and low sulfur while adding a specific ashless antioxidant to the lubricating oil composition and further adding a metal-based antioxidant. Maintaining high-temperature detergency and oxidative stability at a high level by the presence of a metal salt of an organic acid (so-called soap component or soap component) contained in a detergent (a detergent containing a metal component) in a specific range. Of a lubricating oil composition which enables the following. The present invention has been completed based on this new finding.
Accordingly, the present invention relates to a base oil having a sulfur content of 0.1% by weight or less (preferably 0.03% by weight or less) composed of mineral oil and / or synthetic oil, at least based on the total weight of the composition.
a) An ashless dispersant which is an alkenyl or alkyl succinimide or a derivative thereof contains 0.01 to 0.3% by weight in terms of nitrogen content;
b) a metal-containing detergent (so-called metal-based detergent) having a sulfur content of 3% or less and a total base number of 10 to 350 mgKOH / g, in terms of sulfated ash content of 0.1 to 1% by weight;
c) 0.01 to 0.1% by weight of a zinc dialkyldithiophosphate in terms of phosphorus content, and d) 0.01 to 5% by weight of an antioxidant phenol compound and / or an antioxidant amine compound. ,
Wherein the amount of sulfated ash ranges from 0.1 to 1% by weight, the phosphorus content ranges from 0.01 to 0.1% by weight, based on the total weight of the composition, and The sulfur content is in the range of 0.01 to 0.3% by weight, the chlorine content is 40 ppm or less, and the organic acid metal salt contained in the metal-containing detergent contains 0.2 to 7 in the composition. % By weight (preferably 0.5 to 5% by weight, more preferably 1.0 to 3% by weight) of the lubricating oil composition.
本発明の潤滑油組成物において、そのｂ）成分の金属含有清浄剤は、全塩基価３０〜３００ｍｇＫＯＨ／ｇ（特に、３０〜１００ｍｇＫＯＨ／ｇ）の非硫化のアルキルサリチル酸のアルカリ金属塩もしくはアルカリ土類金属塩であることが好ましい。また、本発明のｂ）成分の金属含有清浄剤は、炭素−窒素結合を有する有機酸あるいはフェノール誘導体（特にマンニッヒ塩基構造を有する非硫化のアルキルフェノール誘導体）のアルカリ金属塩もしくはアルカリ土類金属塩であることも好ましい。 In the lubricating oil composition of the present invention, the metal-containing detergent as the component b) is an alkali metal salt or an alkaline earth non-sulfurized alkylsalicylic acid having a total base number of 30 to 300 mgKOH / g (particularly, 30 to 100 mgKOH / g). It is preferably a metal salt. The metal-containing detergent of the component (b) of the present invention is an alkali metal salt or an alkaline earth metal salt of an organic acid or a phenol derivative having a carbon-nitrogen bond (particularly a non-sulfurized alkylphenol derivative having a Mannich base structure). It is also preferred.
本発明の潤滑油組成物において、そのａ）成分の無灰性分散剤は、塩素含有量が３０重量ｐｐｍ以下の無灰性分散剤であることが好ましく、特に、ポリブテンと無水マレイン酸とを原料とし、塩素もしくは塩素含有化合物を接触させることのない熱反応法により得られるポリブテニルこはく酸無水物をポリアミンと反応させて得られるこはく酸イミドあるいはその誘導体であることが好ましい。 In the lubricating oil composition of the present invention, the ashless dispersant of the component a) is preferably an ashless dispersant having a chlorine content of 30% by weight or less, and particularly, a polybutene and maleic anhydride. The raw material is preferably succinimide or a derivative thereof obtained by reacting polybutenylsuccinic anhydride obtained by a thermal reaction method without contacting chlorine or a chlorine-containing compound with a polyamine.
本発明の潤滑油組成物において、組成物の全重量に基づくリン含有量は、０．０６重量％以下であることが好ましく、また組成物の全重量に基づく硫黄含有量が０．１５重量％以下であることが好ましい。 In the lubricating oil composition of the present invention, the phosphorus content based on the total weight of the composition is preferably 0.06% by weight or less, and the sulfur content based on the total weight of the composition is 0.15% by weight. The following is preferred.
本発明の潤滑油組成物において、そのｄ）成分は、ヒンダードフェノール化合物および／またはジアリールアミン化合物であることが好ましく、またさらに、モリブデン含有化合物を０．０１〜５重量％および／または、アルカリ金属ホウ酸塩水和物を０．０１〜５重量％を含有することが好ましい。そして、本発明の潤滑油組成物は、さらに粘度指数向上剤を添加してマルチグレードエンジン油として用いることが有利である。 In the lubricating oil composition of the present invention, the component d) is preferably a hindered phenol compound and / or a diarylamine compound, and further contains a molybdenum-containing compound in an amount of 0.01 to 5% by weight and / or an alkali. It is preferable to contain 0.01 to 5% by weight of metal borate hydrate. It is advantageous that the lubricating oil composition of the present invention is further used as a multi-grade engine oil by adding a viscosity index improver.
本発明の潤滑油組成物は、低硫酸灰分含量、低リン含量、かつ低硫黄含量であるにもかかわらず、現在一般的に利用されている高硫酸灰分、高リン含量かつ高硫黄含量のディーゼルエンジン油と同等もしくはそれ以上の高温清浄性を示している。従って、本発明の潤滑油組成物はは、走行用燃料として、硫黄含有量が約０．０１重量％以下の炭化水素系燃料を用いる自動車、なかでも排ガス浄化装置（特にパティキュレートフィルタおよび酸化触媒）を備えたディーゼルエンジン搭載車においても好適に用いられる。 The lubricating oil composition of the present invention has a low sulfated ash content, a low phosphorus content, and a low sulfur content, but is a high sulfated ash content, a high phosphorus content, and a high sulfur content diesel that is currently generally used. High temperature detergency equivalent to or better than engine oil. Therefore, the lubricating oil composition of the present invention can be used for automobiles using a hydrocarbon-based fuel having a sulfur content of about 0.01% by weight or less as a fuel for traveling, especially an exhaust gas purifying apparatus (particularly, a particulate filter and an oxidation catalyst). ) Is also suitably used in a vehicle equipped with a diesel engine provided with the above.
本発明の潤滑油組成物における基油としては、通常、１００℃における動粘度が２〜５０ｍｍ２／ｓの鉱油や合成油が用いられる。この鉱油や合成油の種類、あるいはその他の性状については特に制限はないが、基油として、硫黄含有量が０．１重量％以下である必要がある。この硫黄含有量は０．０３重量％以下であることが望ましく、特に０．００５重量％以下であることが望ましい。 As the base oil in the lubricating oil composition of the present invention, a mineral oil or a synthetic oil having a kinematic viscosity at 100 ° C of 2 to 50 mm 2 / s is usually used. There are no particular restrictions on the type of mineral oil or synthetic oil or other properties, but the base oil must have a sulfur content of 0.1% by weight or less. The sulfur content is desirably 0.03% by weight or less, and particularly desirably 0.005% by weight or less.
鉱油系基油は、鉱油系潤滑油留分を溶剤精製あるいは水素化処理などの処理方法を適宜組み合わせて利用して処理したものであることが望ましく、特に高度水素化精製（水素化分解）基油（例えば、粘度指数が１００〜１５０、芳香族含有量が５重量％以下、窒素および硫黄の含有量がそれぞれ５０ｐｐｍ以下である基油）が好ましく用いられる。この中には、鉱油系スラックワックス（粗ろう）あるいは天然ガスから合成された合成ワックスを原料として異性化および水素化分解のプロセスで作られる高粘度指数基油が含まれる。水素化分解基油は、低硫黄分、低蒸発性、残留炭素分が少ないなどの点から、本発明の目的上好ましいものである。 The mineral oil-based base oil is desirably a mineral oil-based lubricating oil fraction that has been treated using a suitable combination of treatment methods such as solvent refining or hydrogenation treatment. An oil (for example, a base oil having a viscosity index of 100 to 150, an aromatic content of 5% by weight or less, and a nitrogen and sulfur content of 50 ppm or less, respectively) is preferably used. These include high viscosity index base oils produced by a process of isomerization and hydrocracking using mineral oil-based slack wax (crude wax) or synthetic wax synthesized from natural gas as a raw material. Hydrocracked base oils are preferred for the purpose of the present invention in terms of low sulfur content, low evaporability, and low residual carbon content.
合成油（合成潤滑油基油）としては、例えば炭素数３〜１２のα−オレフィンの重合体であるポリ−α−オレフィン、ジオクチルセバケートに代表されるセバシン酸、アゼライン酸、アジピン酸などの二塩基酸と炭素数４〜１８のアルコールとのエステルであるジアルキルジエステル、１−トリメチロールプロパンやペンタエリスリトールと炭素数３〜１８の一塩基酸とのエステルであるポリオールエステル、炭素数９〜４０のアルキル基を有するアルキルベンゼンなどを挙げることができる。 Examples of synthetic oils (synthetic lubricating base oils) include poly-α-olefins, which are polymers of α-olefins having 3 to 12 carbon atoms, sebacic acid, azelaic acid, and adipic acid represented by dioctyl sebacate. Dialkyl diester which is an ester of a dibasic acid and an alcohol having 4 to 18 carbon atoms; polyol ester which is an ester of 1-trimethylolpropane or pentaerythritol and a monobasic acid having 3 to 18 carbon atoms; And an alkylbenzene having an alkyl group of
一般に合成油は実質的に硫黄分を含まず、酸化安定性、耐熱性に優れ、いったん燃焼すると残留炭素や煤の生成が少ないので、本潤滑油組成物には特に好ましい。 合成 Generally, synthetic oils are particularly preferred for the present lubricating oil compositions because they contain substantially no sulfur, are excellent in oxidation stability and heat resistance, and generate little residual carbon or soot once burned.
鉱油系基油および合成系基油は、それぞれ単独で使用することができるが、所望により、二種以上の鉱油系基油、あるいは二種以上の合成系基油を組合わせて使用することもできる。また、所望により、鉱油系基油と合成系基油とを任意の割合で組合わせて用いることもできる。 The mineral base oil and the synthetic base oil can be used alone, but if desired, two or more mineral base oils or two or more synthetic base oils can be used in combination. it can. If desired, a mineral base oil and a synthetic base oil can be used in combination at any ratio.
本発明の潤滑油組成物におけるａ）成分としての無灰性分散剤としては、ポリオレフィンから誘導されるアルケニルもしくはアルキルこはく酸イミドあるいはその誘導体が用いられる。その添加量は、組成物の全重量に基づき、窒素含有量換算値で、０．０１〜０．３重量％の範囲である。代表的なこはく酸イミドは、高分子量のアルケニルもしくはアルキル基で置換された、こはく酸無水物と１分子当り平均４〜１０個（好ましくは５〜７個）の窒素原子を含むポリアルキレンポリアミンとの反応により得ることができる。高分子量のアルケニルもしくはアルキル基は、数平均分子量が約９００〜３０００のポリブテンであることが好ましい。 ア ル ケ ニ As the ashless dispersant as the component a) in the lubricating oil composition of the present invention, an alkenyl or alkyl succinimide derived from a polyolefin or a derivative thereof is used. The amount of addition is in the range of 0.01 to 0.3% by weight in terms of nitrogen content based on the total weight of the composition. Representative succinimides are succinic anhydrides substituted with high molecular weight alkenyl or alkyl groups and polyalkylene polyamines containing an average of 4 to 10 (preferably 5 to 7) nitrogen atoms per molecule. Can be obtained. Preferably, the high molecular weight alkenyl or alkyl group is a polybutene having a number average molecular weight of about 900-3000.
ポリブテンと無水マレインとの反応により、ポリブテニルこはく酸無水物を得る工程では、多くの場合、塩素を用いる塩素化法が用いられている。しかし、この方法では、こはく酸イミド最終製品中に多量の塩素（例えば約２０００〜３０００ｐｐｍ）が残留する結果となる。一方、塩素を用いない熱反応法では、最終製品中に残る塩素を極めて低いレベル（例えば０〜３０ｐｐｍ）におさえることができる。従って、潤滑油組成物中の塩素含有量を０〜３０重量ｐｐｍの範囲の量に抑えるためには、熱反応法によって得られたポリブテニルこはく酸無水物からのこはく酸イミドを用いることが望ましい。こはく酸イミドは更にホウ酸、アルコール、アルデヒド、ケトン、アルキルフェノール、環状カーボネート、有機酸等と反応させ、いわゆる変性こはく酸イミドにして用いることができる。特に、ホウ酸あるいはホウ素化合物との反応で得られるホウ素含有アルケニル（もしくはアルキル）こはく酸イミドは、熱・酸化安定性の面で有利である。 工程 In the step of obtaining polybutenylsuccinic anhydride by the reaction between polybutene and maleic anhydride, a chlorination method using chlorine is often used. However, this method results in a large amount of chlorine (eg, about 2000-3000 ppm) remaining in the succinimide final product. On the other hand, in the thermal reaction method not using chlorine, the chlorine remaining in the final product can be suppressed to an extremely low level (for example, 0 to 30 ppm). Therefore, in order to suppress the chlorine content in the lubricating oil composition to an amount in the range of 0 to 30 ppm by weight, it is desirable to use succinimide from polybutenylsuccinic anhydride obtained by a thermal reaction method. The succinimide can be further reacted with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid, etc., and used as a so-called modified succinimide. In particular, boron-containing alkenyl (or alkyl) succinimide obtained by reaction with boric acid or a boron compound is advantageous in terms of thermal and oxidation stability.
本発明の潤滑油組成物は、アルケニルもしくはアルキルこはく酸イミドあるいはその誘導体を必須成分として含有するが、これら以外の無灰性分散剤であるアルケニルベンジルアミン系やアルケニルこはく酸エステル系の無灰性分散剤も適宜組合わせて用いられる。 The lubricating oil composition of the present invention contains an alkenyl or alkyl succinimide or a derivative thereof as an essential component, and other ashless dispersants such as alkenylbenzylamine-based and alkenyl succinic ester-based ashless A dispersant is also used in an appropriate combination.
本発明の潤滑油組成物におけるｂ）成分である金属系清浄剤としては、硫黄含有量３％以下で全塩基価１０〜３５０ｍｇＫＯＨ／ｇの金属系清浄剤を硫酸灰分換算値で０．１〜１重量％の範囲で用いる。 As the metal-based detergent which is the component b) in the lubricating oil composition of the present invention, a metal-based detergent having a sulfur content of 3% or less and a total base number of 10 to 350 mgKOH / g is 0.1 to 0.1% in terms of sulfated ash content. Used in the range of 1% by weight.
一般に金属系清浄剤としては、硫化フェネート、石油もしくは合成系スルホネート、サリシレートなどが用いられてきた。本発明の特徴である低灰分、低硫黄を実現し、高温清浄性を維持するためには、金属系清浄剤として、(1)硫黄含有量が小さい、(2)過塩基化度があまり高くない、(3)金属成分として原子量が小さい金属（例えば有利な方からＬｉ、Ｍｇ、Ｃａ、Ｂａの順）を含む、(4)金属に由来する塩基価以上の塩基価が期待できる（例えばアミン反応物）などの性状を持つ金属系清浄剤を用いること望ましい。本発明者は、これらの観点から鋭意検討し、特に、全塩基価が３０〜３００ｍｇＫＯＨ／ｇの非硫化のアルキルサリシレート（アルカリ金属塩もしくはアルカリ土類金属塩）が本発明の目的に有効であることを見出した。金属サリシレートは、通常、平均炭素原子数が約８〜３０のα−オレフィンとフェノールの反応で得られるアルキルフェノールからコルベ・シュミット反応を利用して製造されるアルキルサリチル酸のアルカリ金属塩もしくはアルカリ土類金属塩である。アルカリ土類金属塩は、通常、Ｎａ塩もしくはＫ塩を複分解法あるいは硫酸分解法等により、Ｃａ塩、Ｍｇ塩に転換する。塩化カルシウム（ＣａＣｌ２）等を用いる複分解法は、残留塩素が多くなるので、その点で好ましくない。 Generally, sulfurized phenates, petroleum or synthetic sulfonates, salicylates, and the like have been used as metal-based detergents. In order to realize low ash content and low sulfur which are features of the present invention and to maintain high-temperature detergency, as a metal-based detergent, (1) small sulfur content, (2) the degree of overbasing is too high. (3) Including a metal having a small atomic weight as a metal component (for example, Li, Mg, Ca, and Ba in order of advantage), and (4) A base number derived from the metal or higher can be expected (for example, amine It is desirable to use a metal-based detergent having properties such as a reactant). The present inventor has studied diligently from these viewpoints. In particular, a non-sulfurized alkyl salicylate (alkali metal salt or alkaline earth metal salt) having a total base number of 30 to 300 mgKOH / g is effective for the purpose of the present invention. I found that. Metal salicylates are usually alkali metal salts or alkaline earth metals of alkyl salicylic acids produced from an alkyl phenol obtained by reacting an α-olefin having an average carbon number of about 8 to 30 with phenol by utilizing the Kolbe-Schmidt reaction. Salt. The alkaline earth metal salt usually converts a Na salt or a K salt into a Ca salt or a Mg salt by a double decomposition method or a sulfuric acid decomposition method. The double decomposition method using calcium chloride (CaCl 2 ) or the like is not preferable because residual chlorine increases.
また、アルキルフェノールを直接中和してＣａ塩にし、炭酸化工程で直接カルシウムサリシレートを得る方法もあるが、サリシレートへの変換率がコルベ・シュミット法に比べ劣る。本発明者は、コルベ・シュミット法−硫酸分解法を経て製造される、全塩基価が３０〜３００ｍｇＫＯＨ／ｇ（更に好ましくは、３０〜１００ｍｇＫＯＨ／ｇ）の非硫化のアルキルサリシレートが本発明の目的に特に有効であることを見出した。 Also, there is a method of directly neutralizing an alkylphenol to form a Ca salt and directly obtaining calcium salicylate in the carbonation step, but the conversion rate to salicylate is inferior to that of the Kolbe-Schmidt method. The present inventor has set forth a non-sulfurized alkyl salicylate having a total base number of 30 to 300 mgKOH / g (more preferably 30 to 100 mgKOH / g), which is produced via the Kolbe-Schmidt-sulfuric acid decomposition method. Was found to be particularly effective.
一方、金属系清浄剤として、炭素−窒素結合を有する有機酸あるいはフェノール誘導体のアルカリ金属塩もしくはアルカリ土類金属塩も本発明に有効であることを見出した。一般にアミン化合物を反応させることにより、塩基性の窒素に由来する塩基価が得られ、低灰分でも高い塩基価が得られ有利となる。例えば、アミノカルボン酸の金属塩等のさまざまなものが考えられるが、特に、マンニッヒ塩基構造を有する非硫化のアルキルフェネート（アルカリ金属塩もしくはアルカリ土類金属塩）が本発明に有効であることを見出した。この化合物は、通常、アルキルフェノール、ホルムアルデヒド、アミンあるいはアミン化合物を用い、マンニッヒ反応により合成し、フェノールの環のアミノメチル化により得られる反応物を水酸化カルシウム等の塩基で中和し、金属塩にすることによって得ることができる。具体的には、例えば、次の一般式で表される化合物（Ｒは炭素原子数８〜３０のアルキル基であり、ｎは０あるいは正の整数である）が本発明に有効である。 On the other hand, as a metal-based detergent, an alkali metal salt or an alkaline earth metal salt of an organic acid or a phenol derivative having a carbon-nitrogen bond was also found to be effective in the present invention. In general, by reacting an amine compound, a base number derived from basic nitrogen is obtained, and a high base number is obtained even with a low ash content, which is advantageous. For example, various compounds such as metal salts of aminocarboxylic acids can be considered. In particular, non-sulfurized alkyl phenates having a Mannich base structure (alkali metal salts or alkaline earth metal salts) are effective in the present invention. Was found. This compound is usually synthesized by Mannich reaction using an alkylphenol, formaldehyde, amine or amine compound, and the reaction product obtained by aminomethylation of the phenol ring is neutralized with a base such as calcium hydroxide to form a metal salt. Can be obtained. Specifically, for example, a compound represented by the following general formula (R is an alkyl group having 8 to 30 carbon atoms and n is 0 or a positive integer) is effective in the present invention.
上記一般式の化合物の性状の一例としては、Ｃａ＝２．５重量％、Ｎ＝１．６重量％、全塩基価＝１３５ｍｇＫＯＨ／ｇのものがあり、塩基性の窒素に由来する塩基価が全体の５０％近いことを示している。 An example of the properties of the compound of the above general formula includes Ca = 2.5% by weight, N = 1.6% by weight, total base number = 135 mgKOH / g, and the base number derived from basic nitrogen is It shows that it is close to 50% of the whole.
これまでに述べた金属系清浄剤の他に、石油スルホン酸あるいはアルキルベンゼンスルホン酸のアルカリ金属塩もしくはアルカリ土類金属塩であるスルホネートも有効に用いられる。高温清浄性の面からは、硫酸灰分を一定にしたとき、過塩基価度の小さいスルホネートが有利であることを見出した。この場合、過塩基価度の小さいスルホネートは添加量が多くなり、硫黄含有量を増加させ、又添加量の割には全塩基価が大きくならないので、この点は注意を要する。先に述べたような非硫化のサリシレートやフェネート誘導体と組合わせると、効果的である。 の 他 In addition to the metal-based detergents described above, sulfonates that are alkali metal salts or alkaline earth metal salts of petroleum sulfonic acid or alkylbenzene sulfonic acid are also effectively used. From the viewpoint of high-temperature detergency, it has been found that, when the sulfated ash content is kept constant, a sulfonate having a small overbased number is advantageous. In this case, attention must be paid to the fact that the sulfonate having a small overbasing number increases in amount to increase the sulfur content and that the total base number does not increase in proportion to the amount of addition. It is effective when combined with a non-sulfurized salicylate or phenate derivative as described above.
従来用いられてきた硫化フェネートは、硫化アルキルフェノールのアルカリ金属塩もしくはアルカリ土類金属塩であって、通常、Ｃａ塩あるいはＭｇ塩が知られている。硫化フェネートは、耐熱性が良好であるが、硫化反応に起因する硫黄含有量が約３重量％を越えるものが多い。本発明においては、先に述べたような金属系清浄剤と組合わせて、部分的に用いることができる。特に非硫化のサリシレートと組合わせて用いると効果的であることを見出した。 The conventionally used sulfurized phenates are alkali metal salts or alkaline earth metal salts of sulfurized alkylphenols, and Ca salts or Mg salts are generally known. Sulfurized phenates have good heat resistance, but often have a sulfur content exceeding about 3% by weight due to a sulfurization reaction. In the present invention, it can be partially used in combination with the metal-based detergent described above. In particular, it has been found that it is effective to use it in combination with a non-sulfurized salicylate.
潤滑油添加剤の代表的成分のひとつとして知られている金属系清浄剤（金属含有清浄剤）は、基油中に、有機酸金属塩（一般的に石鹸成分あるいはソープ分と呼ばれている）と、その有機酸金属塩の周囲に凝集している塩基性無機塩微粒子（例、炭酸カルシウム微粒子）を分散状態で含む油性分散物である。本発明者の研究によると、潤滑油組成物への金属含有清浄剤の添加量を減らしても、その潤滑油組成物中の有機酸金属塩の存在量が一定レベル以上に維持されていれば、その潤滑油組成物の高温清浄性（高温環境下でエンジンの内部を清浄に維持する能力）の低下は少ないことが判明した。 Metal-based detergents (metal-containing detergents) known as one of the representative components of lubricating oil additives include organic acid metal salts (generally called soap components or soap components) in a base oil. ), And an organic dispersion in which fine particles of a basic inorganic salt (eg, fine particles of calcium carbonate) aggregated around the metal salt of an organic acid are dispersed. According to the study of the present inventor, even if the amount of the metal-containing detergent added to the lubricating oil composition is reduced, the amount of the organic acid metal salt in the lubricating oil composition is maintained at a certain level or more. It has been found that the lubricating oil composition hardly deteriorates in high-temperature detergency (the ability to keep the inside of an engine clean under a high-temperature environment).
本発明の潤滑油組成物におけるｃ）成分のジアルキルジチオリン酸亜鉛は、リン含有量換算値で０．０１〜０．１重量％の範囲で用いるが、低リン含量と低硫黄含量の観点からは、０．０１〜０．０６重量％の範囲の量で用いることが好ましい。 The zinc dialkyldithiophosphate of component c) in the lubricating oil composition of the present invention is used in the range of 0.01 to 0.1% by weight in terms of phosphorus content, but from the viewpoint of low phosphorus content and low sulfur content. , 0.01 to 0.06% by weight.
ジアルキルジチオリン酸亜鉛は、炭素原子数３〜１８のアルキル基もしくは炭素原子数３〜１８のアルキル基を含むアルキルアリール基を有することが望ましい。特に好ましいのは、摩耗の抑制に特に有効な、炭素原子数３〜１８の第二級アルコールから誘導されたアルキル基、あるいは炭素原子数３〜１８の第一級アルコールと炭素原子数３〜１８の第二級アルコールとの混合物から誘導されたアルキル基を含むジアルキルジチオリン酸亜鉛である。第一級アルコールからのジアルキルジチオリン酸亜鉛は耐熱性に優れる傾向がある。これらのジチオリン酸亜鉛は、単独で用いてもよいが、第二級アルキル基タイプのものおよび／または第一級アルキル基タイプのものを主体とする混合物で用いることが好ましい。 The zinc dialkyldithiophosphate desirably has an alkyl group having 3 to 18 carbon atoms or an alkylaryl group containing an alkyl group having 3 to 18 carbon atoms. Particularly preferred are an alkyl group derived from a secondary alcohol having 3 to 18 carbon atoms, or a primary alcohol having 3 to 18 carbon atoms and a primary alcohol having 3 to 18 carbon atoms, which are particularly effective in suppressing wear. Is a zinc dialkyldithiophosphate containing an alkyl group derived from a mixture with a secondary alcohol. Zinc dialkyldithiophosphates from primary alcohols tend to have excellent heat resistance. These zinc dithiophosphates may be used alone, but are preferably used in a mixture mainly composed of a secondary alkyl group type and / or a primary alkyl group type.
本発明の潤滑油組成物は、ｄ）成分として、酸化防止性のフェノール化合物および／または酸化防止性のアミン化合物を０．０１〜５重量％（好ましくは０．１〜３重量％）の範囲で含むことを特徴とする。一般に、低灰分、低リンかつ低硫黄の潤滑油組成物は、金属系清浄剤およびジチオリン酸亜鉛の低減を意味し、高温清浄性や酸化安定性あるいは耐摩耗性の低下につながる。これらの性能を維持するためにｄ）成分が必要となる。このｄ）成分としては、ジアリールアミン系酸化防止剤及び／またはヒンダードフェノール系酸化防止剤が好ましい。これらの酸化防止剤は高温清浄性の向上にも効果的である。特にジアリールアミン系酸化防止剤は、窒素に由来する塩基価を有しているので、この点で有利である。一方、ヒンダードフェノール系酸化防止剤は、ＮＯＸ酸化劣化の防止に有利である。 The lubricating oil composition of the present invention contains, as component d), an antioxidant phenol compound and / or an antioxidant amine compound in an amount of 0.01 to 5% by weight (preferably 0.1 to 3% by weight). It is characterized by including. Generally, a lubricating oil composition having a low ash content, a low phosphorus content and a low sulfur content means a reduction in the amount of a metallic detergent and zinc dithiophosphate, which leads to a decrease in high-temperature detergency, oxidation stability or abrasion resistance. In order to maintain these performances, the component d) is required. As the component (d), a diarylamine antioxidant and / or a hindered phenol antioxidant are preferable. These antioxidants are also effective in improving high-temperature detergency. In particular, a diarylamine-based antioxidant is advantageous in this point because it has a base number derived from nitrogen. On the other hand, hindered phenolic antioxidant is advantageous in prevention of the NO X oxidative degradation.
ヒンダードフェノール酸化防止剤の例としては、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、４，４’−メチレンビス（６−ｔ−ブチル−ｏ−クレゾール）、４，４’−イソプロピリデンビス（２，６−ジ−ｔ−ブチルフェノール）、４，４’−ビス（２，６−ジ−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（２−メチル−６−ｔ−ブチルフェノール）、２，２−チオ−ジエチレンビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、そして３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオン酸オクチル、３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオン酸オクタデシルなどのヒンダードフェノール類を挙げることができる。 Examples of hindered phenol antioxidants include 2,6-di-t-butyl-p-cresol, 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-methylenebis ( 6-t-butyl-o-cresol), 4,4′-isopropylidenebis (2,6-di-t-butylphenol), 4,4′-bis (2,6-di-t-butylphenol), , 2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], and octyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (3,5-di-t-butyl) -4- It may be mentioned hindered phenols such as hydroxyphenyl) octadecyl propionate.
ジアリールアミン酸化防止剤の例としては、炭素原子数が４〜９の混合アルキルジフェニルアミン、ｐ，ｐ’−ジオクチルジフェニルアミン、フェニル−α−ナフチルアミン、フェニル−β−ナフチルアミン、アルキル化−α−ナフチルアミン、そしてアルキル化−フェニル−α−ナフチルアミンなどのジアリールアミン類を挙げることができる。ヒンダードフェノール酸化防止剤とジアリールアミン系酸化防止剤とは、それぞれ単独で使用することができるが、所望により組合せて使用する。また、これら以外の油溶性酸化防止剤を併用してもよい。 Examples of diarylamine antioxidants include mixed alkyl diphenylamines having 4 to 9 carbon atoms, p, p'-dioctyldiphenylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, alkylated-α-naphthylamine, and Examples include diarylamines such as alkylated-phenyl-α-naphthylamine. The hindered phenol antioxidant and the diarylamine-based antioxidant can be used alone, but may be used in combination as desired. Further, other oil-soluble antioxidants may be used in combination.
本発明の潤滑油組成物はさらに、多機能添加剤に属するモリブデン含有化合物および／またはアルカリ金属ホウ酸塩水和物を各々５重量％以下、特に０．０１〜５重量％含有することができる。これらの化合物は灰分あるいは硫黄分等を含むものが多いが、本発明の潤滑油組成物全体の性状を考慮しながら、添加量を調整し効果的に使用することができる。 The lubricating oil composition of the present invention may further contain a molybdenum-containing compound and / or an alkali metal borate hydrate belonging to the multifunctional additive in an amount of 5% by weight or less, particularly 0.01 to 5% by weight. Many of these compounds contain an ash content or a sulfur content, but can be used effectively by adjusting the amount added in consideration of the properties of the entire lubricating oil composition of the present invention.
上記のモリブデン含有化合物は、潤滑油組成物中で、主として摩擦調整剤、酸化防止剤あるいは摩耗防止剤として機能し、また高温での清浄性の向上に寄与する。モリブデン含有化合物の潤滑油組成物中の含有量は、モリブデン金属含有量換算で１０〜２５００ｐｐｍの範囲にあることが望ましい。モリブデン含有化合物の例としては、こはく酸イミドの硫黄含有モリブデン錯体（特公平３−２２４３８号公報に記載）、硫化オキシモリブデンジチオカーバメート、硫化オキシモリブデンジチオホスフェート、アミンモリブデン錯体化合物、オキシモリブデンジエチラートアミド、そしてオキシモリブデンモノグリセリドを挙げることができる。特に、こはく酸イミドの硫黄含有モリブデン錯体は高温での清浄性向上に効果的である。 The above-mentioned molybdenum-containing compound mainly functions as a friction modifier, an antioxidant or an antiwear agent in the lubricating oil composition, and also contributes to improvement in cleanliness at high temperatures. The content of the molybdenum-containing compound in the lubricating oil composition is preferably in the range of 10 to 2500 ppm in terms of molybdenum metal content. Examples of the molybdenum-containing compound include a sulfur-containing molybdenum complex of succinimide (described in JP-B-3-22438), oxymolybdenum dithiocarbamate, oxymolybdenum dithiophosphate, amine molybdenum complex compound, oxymolybdenum dielate amide And oxymolybdenum monoglycerides. In particular, a sulfur-containing molybdenum complex of succinimide is effective in improving cleanliness at high temperatures.
一方、アルカリ金属ホウ酸塩水和物の添加も、高温清浄性あるいは塩基価の付与の点で効果的である。本発明でいうアルカリ金属ホウ酸塩水和物は、米国特許３９２９６５０および４０８９７９０に記載されている方法により合成される化合物に代表される化合物を表す。例えば、アルカリ金属またはアルカリ土類金属中性スルホネートをアルカリ金属水酸化物の存在下で炭酸化して過塩基性スルホネートを得、これにホウ酸を反応させて得られるアルカリ金属ホウ酸塩の微粒子分散体（炭酸化反応の時、こはく酸イミドのような無灰性分散剤を共存させるのが望ましい）を挙げることができる。ここでアルカリ金属としては、カリウム、ナトリウムなどが望ましい。具体例として、中性カルシウムスルホネートおよびこはく酸イミド系に分散させた組成式：ＫＢ3０5・Ｈ2Ｏで表される粒径約０．３μｍ以下の微粒子分散体を挙げることができる。耐水性の点からは、カリウムをナトリウムで置換したものも良好に用いられる。 On the other hand, addition of an alkali metal borate hydrate is also effective in imparting high-temperature detergency or a base number. The alkali metal borate hydrate referred to in the present invention represents a compound represented by a compound synthesized by the method described in US Pat. Nos. 3,929,650 and 4,089,790. For example, an alkali metal or alkaline earth metal neutral sulfonate is carbonated in the presence of an alkali metal hydroxide to obtain an overbased sulfonate, and a fine particle dispersion of an alkali metal borate obtained by reacting boric acid with the overbased sulfonate. (In the case of the carbonation reaction, it is desirable to coexist with an ashless dispersant such as succinimide). Here, potassium or sodium is desirable as the alkali metal. As a specific example, a fine particle dispersion having a particle size of about 0.3 μm or less represented by a composition formula: KB 3 0 5 .H 2 O dispersed in neutral calcium sulfonate and succinimide can be given. From the viewpoint of water resistance, those obtained by replacing potassium with sodium are also used favorably.
本発明の潤滑油組成物は更に、粘度指数向上剤を２０重量％以下（好ましくは１〜２０重量％の範囲）の量で含むことが望ましい。粘度指数向上剤の例としては、ポリアルキルメタクリレート、エチレン−プロピレン共重合体、スチレン−ブタジエン共重合体、そしてポリイソプレンなどの高分子化合物を挙げることができる。あるいは、これらの高分子化合物に分散性能を付与した分散型粘度指数向上剤もしくは多機能型粘度指数向上剤を用いることができる。これらの粘度指数向上剤は単独で用いることができるが、任意の粘度指数向上剤を二種以上を組合せて使用しても良い。 It is desirable that the lubricating oil composition of the present invention further contains a viscosity index improver in an amount of 20% by weight or less (preferably in the range of 1 to 20% by weight). Examples of the viscosity index improver include high molecular compounds such as polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. Alternatively, a dispersion type viscosity index improver or a multi-function type viscosity index improver obtained by imparting dispersibility to these polymer compounds can be used. These viscosity index improvers can be used alone, but any viscosity index improver may be used in combination of two or more.
本発明の潤滑油組成物は更に、各種の補助的な添加剤を含んでいてもよい。そのような補助的な添加剤の例としては、酸化防止剤あるいは摩耗防止剤として、亜鉛ジチオカーバメート、メチレンビス（ジブチルジチオカーバメート）、油溶性銅化合物、硫黄系化合物（例、硫化オレフィン、硫化エステル、ポリスルフィド）、リン酸エステル、亜リン酸エステル、有機アミド化合物（例、オレイルアミド）などを挙げることができる。また金属不活性剤として機能するベンゾトリアゾール系化合物やチアジアゾール系化合物などの化合物を添加することもできる。また、防錆剤あるいは抗乳化剤として機能するポリオキシエチレンアルキルフェニルエーテル、エチレンオキシドとプロピレンオキシドとの共重合体などのポリオキシアルキレン非イオン性の界面活性剤を添加することもできる。また、摩擦調整剤として機能する各種アミン、アミド、アミン塩、およびそれらの誘導体、あるいは多価アルコールの脂肪酸エステル、あるいはそれらの誘導体を添加することもできる。さらにまた、消泡剤や流動点降下剤として機能する各種化合物を添加することもできる。なお、これらの補助的な添加剤は、潤滑油組成物に対して、それぞれ３重量％以下（特に、０．００１〜３重量％の範囲）の量にて使用することが望ましい。 潤滑 The lubricating oil composition of the present invention may further contain various auxiliary additives. Examples of such auxiliary additives include zinc dithiocarbamate, methylenebis (dibutyldithiocarbamate), oil-soluble copper compounds, sulfur-based compounds (eg, sulfurized olefins, sulfurized esters, antioxidants or antiwear agents). Polysulfide), a phosphoric ester, a phosphite, an organic amide compound (eg, oleylamide) and the like. Further, a compound such as a benzotriazole-based compound or a thiadiazole-based compound that functions as a metal deactivator can also be added. In addition, a polyoxyalkylene nonionic surfactant such as polyoxyethylene alkyl phenyl ether, a copolymer of ethylene oxide and propylene oxide, which functions as a rust preventive or a demulsifier, can also be added. In addition, various amines, amides, amine salts, and derivatives thereof that function as friction modifiers, or fatty acid esters of polyhydric alcohols, or derivatives thereof can also be added. Furthermore, various compounds functioning as antifoaming agents and pour point depressants can also be added. These auxiliary additives are preferably used in an amount of 3% by weight or less (particularly in the range of 0.001 to 3% by weight) with respect to the lubricating oil composition.
（１）潤滑油組成物の製造
本発明に従う潤滑油組成物と比較用の潤滑油組成物を、下記の添加剤成分と基油成分とを用いて製造した。これらの潤滑油組成物は、粘度指数向上剤の添加により、１０Ｗ３０の粘度グレード（ＳＡＥ粘度グレード）を示すように調製された。
(1) Production of lubricating oil composition A lubricating oil composition according to the present invention and a lubricating oil composition for comparison were produced using the following additive component and base oil component. These lubricating oil compositions were prepared to show a viscosity grade of 10W30 (SAE viscosity grade) by adding a viscosity index improver.
（２）添加剤及び基油
分散剤Ａ：こはく酸イミド系分散剤（窒素含量：１．６重量％、塩素含量：５重量ｐｐｍ未満、数平均分子量が約１３００のポリブテンと無水マレイン酸とから熱反応法で製造したものに、平均窒素原子数が６．５個（１分子当り）のポリアルキレンポリアミンを反応させて得たもの）
(2) Additives and base oil Dispersant A: succinimide-based dispersant (nitrogen content: 1.6% by weight, chlorine content: less than 5% by weight, polybutene having a number average molecular weight of about 1300 and maleic anhydride) (A product obtained by reacting a polyalkylene polyamine having an average number of nitrogen atoms of 6.5 (per molecule) with a product produced by a thermal reaction method)
分散剤Ｂ：ホウ素含有こはく酸イミド系分散剤（窒素含量：１．５重量％、ホウ素含量：０．５重量％、塩素含量：５重量ｐｐｍ未満、数平均分子量が約１３００のポリブテンと無水マレイン酸とから熱反応法で製造し、これを平均窒素原子数６．５個（１分子当り）のポリアルキレンポリアミンと反応させ、ついで得られたこはく酸イミドをホウ酸で反応処理したもの；特開平７−１５０１６６号公報の実施例８に従って製造したもの） Dispersant B: Boron-containing succinimide dispersant (nitrogen content: 1.5% by weight, boron content: 0.5% by weight, chlorine content: less than 5 ppm by weight, polybutene having a number average molecular weight of about 1300 and anhydrous maleic) An acid is produced by a thermal reaction method, which is reacted with a polyalkylenepolyamine having an average number of nitrogen atoms of 6.5 (per molecule), and then the resulting succinimide is treated with boric acid; (Manufactured according to Example 8 of Kaihei 7-150166)
分散剤Ｃ：炭酸エチレン反応処理こはく酸イミド系分散剤（窒素含量：０．８５重量％、塩素含量：３０重量ｐｐｍ、数平均分子量約２２００のポリブテンと無水マレイン酸とから熱反応法で製造し、これを平均原子数６．５個（１分子当り）のポリアルキレンポリアミンと反応させ、ついで得られたこはく酸イミドを炭酸エチレンで反応処理したもの；特開平７−１５０１６６号公報の実施例１７に従って製造） Dispersant C: ethylene carbonate reaction-treated succinimide dispersant (produced by thermal reaction from polybutene having a nitrogen content of 0.85% by weight, a chlorine content of 30% by weight, a number average molecular weight of about 2200 and maleic anhydride). This is reacted with a polyalkylene polyamine having an average number of atoms of 6.5 (per molecule), and the resulting succinimide is treated with ethylene carbonate; Example 17 of JP-A-7-150166. Manufactured according to)
清浄剤Ａ：カルシウムサリシレート（Ｃａ：２．１重量％、Ｓ：０．１３重量％、ＴＢＮ：６０ｍｇＫＯＨ／ｇ、オスカ化学（株）製ＯＳＣＡ４３１Ｂ）
清浄剤Ｂ：カルシウムサリシレート（Ｃａ：８．２重量％、Ｓ：０．１３重量％、ＴＢＮ：２３０ｍｇＫＯＨ／ｇ、オスカ化学（株）製ＯＳＣＡ４３５Ｂ）
清浄剤Ｃ：マグネシウムサリシレート（Ｍｇ：６．０重量％、Ｓ：０．２２重量％、ＴＢＮ：２８０ｍｇＫＯＨ／ｇ、シェルジャパン（株）製ＳＡＰ００８）
清浄剤Ｄ：カルシウムスルホネート（Ｃａ：２．４重量％、Ｓ：２．９重量％、ＴＢＮ：１７ｍｇＫＯＨ／ｇ、オロナイトジャパン（株）ＯＬＯＡ２４６Ｓ）
清浄剤Ｅ：カルシウムスルホネート（Ｃａ：１２．８重量％、Ｓ：２．０重量％、ＴＢＮ：３２５ｍｇＫＯＨ／ｇ、オロナイトジャパン（株）製ＯＬＯＡ２４７Ｚ）
清浄剤Ｆ：カルシウムスルホネート（Ｃａ：１５．５重量％、Ｓ：１．６重量％、ＴＢＮ：４１０ｍｇＫＯＨ／ｇ、オロナイトジャパン（株）製ＯＬＯＡ２４９Ｓ）
清浄剤Ｇ：硫化カルシウムフェネート（Ｃａ：４．３重量％、Ｓ：５．５重量％、ＴＢＮ：１２０ｍｇＫＯＨ／ｇ、オロナイトジャパン（株）製ＯＬＯＡ２１６Ｑ）
清浄剤Ｈ：硫化カルシウムフェネート（Ｃａ：９．３重量％、Ｓ：３．４重量％、ＴＢＮ：２５５ｍｇＫＯＨ／ｇ、オロナイトジャパン（株）製ＯＬＯＡ２１９）
清浄剤Ｉ：マンニッヒ塩基カルシウムフェネート（Ｃａ：２．５重量％、Ｎ：１．６重量％、Ｓ：０．１重量％、ＴＢＮ：１３５ｍｇＫＯＨ／ｇ、オロナイトジャパン（株）製ＯＬＯＡ２２４）
Detergent A: calcium salicylate (Ca: 2.1% by weight, S: 0.13% by weight, TBN: 60 mg KOH / g, OSCA431B manufactured by Oska Chemical Co., Ltd.)
Detergent B: Calcium salicylate (Ca: 8.2% by weight, S: 0.13% by weight, TBN: 230mgKOH / g, OSCA435B manufactured by Oska Chemical Co., Ltd.)
Detergent C: magnesium salicylate (Mg: 6.0% by weight, S: 0.22% by weight, TBN: 280mgKOH / g, SAP008 manufactured by Shell Japan K.K.)
Detergent D: calcium sulfonate (Ca: 2.4% by weight, S: 2.9% by weight, TBN: 17mgKOH / g, OLONITE JAPAN K.K. OLOA246S)
Detergent E: calcium sulfonate (Ca: 12.8% by weight, S: 2.0% by weight, TBN: 325 mg KOH / g, OLOA247Z manufactured by Oronite Japan K.K.)
Detergent F: Calcium sulfonate (Ca: 15.5% by weight, S: 1.6% by weight, TBN: 410 mgKOH / g, OLOA249S manufactured by Oronite Japan K.K.)
Detergent G: calcium sulfide phenate (Ca: 4.3% by weight, S: 5.5% by weight, TBN: 120 mgKOH / g, OLOA216Q manufactured by Oronite Japan K.K.)
Detergent H: Calcium sulfide phenate (Ca: 9.3% by weight, S: 3.4% by weight, TBN: 255mgKOH / g, OLOA219 manufactured by Oronite Japan K.K.)
Detergent I: Mannich base calcium phenate (Ca: 2.5% by weight, N: 1.6% by weight, S: 0.1% by weight, TBN: 135 mgKOH / g, OLOA224 manufactured by Oronite Japan K.K.)
ＺｎＤＴＰ：ジアルキルジチオリン酸亜鉛（Ｐ：７．２重量％、Ｚｎ：７．８５％、Ｓ：１４．４％、原料として炭素原子数３〜８の第二級アルコールを使用）
酸化防止剤Ａ：アミン系化合物〔ジアルキルジフェニルアミン（アルキル基：Ｃ4とＣ8の混合）、Ｎ：４．６重量％、ＴＢＮ：１８０ｍｇＫＯＨ／ｇ〕
酸化防止剤Ｂ：フェノール系化合物〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオン酸オクチル〕
Ｍｏ化合物：硫黄を含有するオキシモリブデン−こはく酸イミド錯体化合物（Ｍｏ：５．４重量％、Ｓ：３．７重量％、ＴＢＮ：４５ｍｇＫＯＨ／ｇ）
アルカリ金属ホウ酸塩：ホウ酸カリウム水和物の微粒子分散体（実験式ＫＢ３Ｏ５・Ｈ２Ｏ、Ｋ：８．３重量％、Ｂ：６．８重量％、Ｓ：０．２６重量％、ＴＢＮ：１２５ｍｇＫＯＨ／ｇ）
ZnDTP: zinc dialkyldithiophosphate (P: 7.2% by weight, Zn: 7.85%, S: 14.4%, using a secondary alcohol having 3 to 8 carbon atoms as a raw material)
Antioxidant A: amine compound [dialkyldiphenylamine (alkyl group: mixture of C 4 and C 8 ), N: 4.6% by weight, TBN: 180 mgKOH / g]
Antioxidant B: phenolic compound [octyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
Mo compound: Oxymolybdenum-succinimide complex compound containing sulfur (Mo: 5.4% by weight, S: 3.7% by weight, TBN: 45 mgKOH / g)
Alkali metal borate: fine particle dispersion of potassium borate hydrate (empirical formula KB 3 O 5 .H 2 O, K: 8.3% by weight, B: 6.8% by weight, S: 0.26% by weight %, TBN: 125 mgKOH / g)
ＶＩＩ：粘度指数向上剤（非分散型のエチレンプロピレン共重合体、Ｐａｒａｔｏｎｅ８０５７）
ＰＰＤ：流動点降下剤（ポリメタクリレート系）
VII: Viscosity index improver (non-dispersible ethylene propylene copolymer, Paratone 8057)
PPD: Pour point depressant (polymethacrylate)
基油Ａ：１００℃における動粘度が６．５ｍｍ２／ｓで、粘度指数が１３２、硫黄含有量が０．００１重量％未満の高度水素化精製基油
基油Ｂ：１００℃における動粘度が１１．０ｍｍ２／ｓで、粘度指数が１０４、硫黄含有量が０．００１重量％未満の水素化精製基油
基油Ｃ：１００℃における動粘度が５．３ｍｍ２／ｓで、粘度指数が１０１、硫黄含有量が０．２１重量％の溶剤精製基油
Base oil A: a highly hydrorefined base oil having a kinematic viscosity at 100 ° C. of 6.5 mm 2 / s, a viscosity index of 132, and a sulfur content of less than 0.001% by weight Base oil B: a kinematic viscosity at 100 ° C. in 11.0 mm 2 / s, viscosity index of 104, a sulfur content of oil hydrotreated base oil groups of less than 0.001 wt% C: kinematic viscosity at 100 ° C. is at 5.3 mm 2 / s, viscosity index 101, a solvent refined base oil having a sulfur content of 0.21% by weight
（３）潤滑油組成物の高温清浄性の評価
下記の方法に従うホットチューブ試験（ＫＥＳ−０７−８０３）により、潤滑油組成物の高温での清浄性能を評価した。
内径２ｍｍのガラス管に垂直にヒーターブロックにセットし、試料油を０．３１ｃｃ／時間、そして空気を１０ｃｃ／分の割合で、それぞれガラス管の下部より送り込む。この操作を、ヒーター部の温度を２９０℃あるいは３００℃に保ちながら、１６時間続ける。試験終了後のガラス管内部に付着したデポジット（堆積物）を１０点満点で評価する（１０点がデポジットの堆積がない状態を意味する。）
（４）有機酸金属塩含量（石鹸分）の測定
通常のゴム膜透析法により、金属系清浄剤中の鉱油分および低分子量成分を透析させ、ゴム膜中に残存する清浄剤有効成分である透析残渣（Ａ）を得る。一方、金属系清浄剤中の炭酸塩に由来する二酸化炭素の測定を行い、これと金属分析をもとに、炭酸カルシウムあるいは炭酸マグネシウム等の過塩基性成分（Ｂ）を求める。この（Ａ）と（Ｂ）の差から有機酸金属塩（石鹸分）を求めた。
(3) Evaluation of high-temperature detergency of lubricating oil composition A high-temperature detergency of the lubricating oil composition was evaluated by a hot tube test (KES-07-803) according to the following method.
The sample block is set perpendicularly to a glass tube having an inner diameter of 2 mm in a heater block, and the sample oil is fed from the lower portion of the glass tube at a rate of 0.31 cc / hour and air at a rate of 10 cc / minute. This operation is continued for 16 hours while maintaining the temperature of the heater section at 290 ° C. or 300 ° C. Deposits (deposits) adhering to the inside of the glass tube after the test are evaluated on a scale of 10 out of 10 (10 points means a state where no deposits are deposited).
(4) Measurement of organic acid metal salt content (soap content) Mineral oil and low molecular weight components in the metal-based detergent are dialyzed by a normal rubber membrane dialysis method, and are detergent active components remaining in the rubber membrane. The dialysis residue (A) is obtained. On the other hand, carbon dioxide derived from the carbonate in the metal-based detergent is measured, and an overbased component (B) such as calcium carbonate or magnesium carbonate is determined based on the measurement and the metal analysis. The organic acid metal salt (soap) was determined from the difference between (A) and (B).
［実施例１］本発明の潤滑剤組成物の配合（ＴＢＮ：７．０ｍｇＫＯＨ／ｇ）
（１）無灰性分散剤：
分散剤Ｂ（添加量：４重量％、窒素量換算添加量：０．０６重量％）
分散剤Ｃ（添加量：１．２重量％、窒素量換算添加量：０．０１重量％）
（２）金属系清浄剤：
清浄剤Ａ（添加量：６．９重量％、硫酸灰分換算添加量：０．４９重量％、
有機酸金属塩換算添加量：２．５重量％）
（３）ＺｎＤＴＰ
（添加量：０．４２重量％、リン量換算添加量：０．０３重量％）
（４）酸化防止剤
酸化防止剤Ａ（添加量：０．７重量％）
酸化防止剤Ｂ（添加量：０．７重量％）
（５）他の添加剤
Ｍｏ化合物（添加量：０．１重量％）
アルカリ金属ホウ酸塩（添加量：０重量％）
ＶＩＩ（添加量：２．０重量％）
ＰＰＤ（添加量：０．３重量％）
（６）基油
基油Ａ（使用量：６２．４重量％）
基油Ｂ（使用量：２０．８重量％）
[Example 1] Formulation of the lubricant composition of the present invention (TBN: 7.0 mgKOH / g)
(1) Ashless dispersant:
Dispersant B (addition amount: 4% by weight, added amount in terms of nitrogen amount: 0.06% by weight)
Dispersant C (addition amount: 1.2% by weight, addition amount in terms of nitrogen amount: 0.01% by weight)
(2) Metal detergent:
Detergent A (addition amount: 6.9% by weight, sulfated ash equivalent addition amount: 0.49% by weight,
Organic acid metal salt equivalent: 2.5% by weight)
(3) ZnDTP
(Addition amount: 0.42% by weight, phosphorus equivalent conversion amount: 0.03% by weight)
(4) Antioxidant Antioxidant A (addition amount: 0.7% by weight)
Antioxidant B (addition amount: 0.7% by weight)
(5) Other additives Mo compound (addition amount: 0.1% by weight)
Alkali metal borate (addition amount: 0% by weight)
VII (addition amount: 2.0% by weight)
PPD (addition amount: 0.3% by weight)
(6) Base oil Base oil A (use amount: 62.4% by weight)
Base oil B (Amount used: 20.8% by weight)
［実施例２］本発明の潤滑剤組成物の配合（ＴＢＮ：６．９ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａの代わりに清浄剤Ｂを、添加量：１．８重量％（硫酸灰分換算添加量：０．４９重量％、有機酸金属塩換算添加量：０．７重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６６．４重量％と２２．２重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 2] Formulation of the lubricant composition of the present invention (TBN: 6.9 mgKOH / g)
As a metal-based detergent, detergent B was added instead of detergent A in an amount of 1.8% by weight (addition amount in terms of sulfated ash: 0.49% by weight, addition amount in terms of organic acid metal salt: 0.7%) %), And 66.4% by weight and 22.2% by weight of a base oil A and a base oil B were used as base oils, respectively, to prepare a lubricating oil composition having the same composition as in Example 1. did.
［実施例３］本発明の潤滑剤組成物の配合（ＴＢＮ：７．５ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａの代わりに清浄剤Ｃを、添加量：１．７重量％（硫酸灰分換算添加量：０．４９重量％、有機酸金属塩換算添加量：０．４重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６６．８重量％と２２．３重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 3] Formulation of the lubricant composition of the present invention (TBN: 7.5 mgKOH / g)
As a metal-based detergent, detergent C instead of detergent A was added in an amount of 1.7% by weight (addition amount in terms of sulfated ash: 0.49% by weight, addition amount in terms of organic acid metal salt: 0.4%) %), And 66.8% by weight and 22.3% by weight of base oils A and B were used as base oils, respectively, to prepare a lubricating oil composition having the same composition as in Example 1. did.
［実施例４］本発明の潤滑剤組成物の配合（ＴＢＮ：１４．７ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａの代わりに清浄剤Ｉを、添加量：５．８重量％（硫酸灰分換算添加量：０．４９重量％、有機酸金属塩換算添加量：２．３重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６３．３重量％と２１．１重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
Example 4 Formulation of the lubricant composition of the present invention (TBN: 14.7 mgKOH / g)
As a metal-based detergent, detergent I was added instead of detergent A, in an amount of 5.8% by weight (addition amount in terms of sulfated ash: 0.49% by weight, addition amount in terms of organic acid metal salt: 2.3%) %), And 63.3% by weight and 21.1% by weight of base oils A and B were used as base oils, respectively, to prepare a lubricating oil composition having the same composition as in Example 1. did.
［実施例５］本発明の潤滑剤組成物の配合（ＴＢＮ：３．９ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａの代わりに清浄剤Ｄを、添加量：６．１重量％（硫酸灰分換算添加量：０．４９重量％、有機酸金属塩換算添加量：２．９重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６３．０重量％と２１．０重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 5] Formulation of the lubricant composition of the present invention (TBN: 3.9 mgKOH / g)
As a metal-based detergent, detergent D instead of detergent A, added amount: 6.1% by weight (added amount in terms of sulfated ash: 0.49% by weight, added amount in terms of organic acid metal salt: 2.9%) %), And lubricating oil compositions were prepared in the same formulation as in Example 1 except that 63.0% by weight and 21.0% by weight of base oils A and B were used as base oils, respectively. did.
［実施例６］本発明の潤滑剤組成物の配合（ＴＢＮ：６．５ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａの代わりに清浄剤Ｅを、添加量：１．１重量％（硫酸灰分換算添加量：０．４９重量％、有機酸金属塩換算添加量：０．２重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６７．０重量％と２２．３重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 6] Formulation of the lubricant composition of the present invention (TBN: 6.5 mgKOH / g)
As a metal-based detergent, a detergent E is added instead of the detergent A in an amount of 1.1% by weight (addition amount in terms of sulfated ash: 0.49% by weight, addition amount in terms of organic acid metal salt: 0.2%) %), And 67.0% by weight and 22.3% by weight of base oils A and B were used as base oils, respectively, to prepare a lubricating oil composition having the same composition as in Example 1. did.
［実施例７］本発明の潤滑剤組成物の配合（ＴＢＮ：７．５ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａを、添加量：５．９重量％（硫酸灰分換算添加量：０．４２重量％、有機酸金属塩換算添加量：２．１重量％）にて、そして清浄剤Ｉを、添加量：０．８２重量％（硫酸灰分換算添加量：０．０７重量％、有機酸金属塩換算添加量：０．３重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６２．５重量％と２０．９重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 7] Formulation of the lubricant composition of the present invention (TBN: 7.5 mgKOH / g)
As a metal-based detergent, detergent A was added in an amount of 5.9% by weight (addition amount in terms of sulfated ash: 0.42% by weight, addition amount in terms of organic acid metal salt: 2.1% by weight), and Detergent I was added in an addition amount of 0.82% by weight (addition amount in terms of sulfated ash: 0.07% by weight, addition amount in terms of organic acid metal salt: 0.3% by weight), and as a base oil, A lubricating oil composition was prepared in the same formulation as in Example 1 except that 62.5% by weight and 20.9% by weight of oil A and base oil B were used, respectively.
［実施例８］本発明の潤滑剤組成物の配合（ＴＢＮ：６．９ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａを、添加量：５．９重量％（硫酸灰分換算添加量：０．４２重量％、有機酸金属塩換算添加量：２．１重量％）にて、そして清浄剤Ｇを、添加量：０．４９重量％（硫酸灰分換算添加量：０．０７重量％、有機酸金属塩換算添加量：０．２重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６２．８重量％と２０．９重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 8] Formulation of the lubricant composition of the present invention (TBN: 6.9 mgKOH / g)
As a metal-based detergent, detergent A was added in an amount of 5.9% by weight (addition amount in terms of sulfated ash: 0.42% by weight, addition amount in terms of organic acid metal salt: 2.1% by weight), and Detergent G was added in an amount of 0.49% by weight (addition amount in terms of sulfated ash: 0.07% by weight, addition amount in terms of organic acid metal salt: 0.2% by weight). A lubricating oil composition was prepared with the same formulation as in Example 1, except that 62.8% by weight and 20.9% by weight of oil A and base oil B were used, respectively.
［実施例９］本発明の潤滑剤組成物の配合（ＴＢＮ：６．５ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａを、添加量：５．９重量％（硫酸灰分換算添加量：０．４２重量％、有機酸金属塩換算添加量：２．１重量％）にて、そして清浄剤Ｄを、添加量：０．８８重量％（硫酸灰分換算添加量：０．０７重量％、有機酸金属塩換算添加量：０．４重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６２．５重量％と２０．８重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 9] Formulation of the lubricant composition of the present invention (TBN: 6.5 mgKOH / g)
As a metal-based detergent, detergent A was added in an amount of 5.9% by weight (addition amount in terms of sulfated ash: 0.42% by weight, addition amount in terms of organic acid metal salt: 2.1% by weight), and Detergent D was added in an amount of 0.88% by weight (addition amount in terms of sulfated ash: 0.07% by weight, addition amount in terms of organic acid metal salt: 0.4% by weight). A lubricating oil composition was prepared with the same formulation as in Example 1 except that 62.5% by weight and 20.8% by weight of oil A and base oil B were used, respectively.
［実施例１０］本発明の潤滑剤組成物の配合（ＴＢＮ：７．０ｍｇＫＯＨ／ｇ）
Ｍｏ化合物の添加量を０．２重量％に変え、基油として、基油Ａと基油Ｂとをそれぞれ６２．３重量％と２０．８重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 10] Formulation of the lubricant composition of the present invention (TBN: 7.0 mgKOH / g)
The same formulation as in Example 1 was used except that the addition amount of the Mo compound was changed to 0.2% by weight, and as base oils, 62.3% by weight and 20.8% by weight of base oil A and base oil B were used, respectively. To prepare a lubricating oil composition.
［実施例１１］本発明の潤滑剤組成物の配合（ＴＢＮ：７．３ｍｇＫＯＨ／ｇ）
さらに、アルカリ金属ホウ酸塩を０．３重量％加え、基油として、基油Ａと基油Ｂとをそれぞれ６２．２重量％と２０．７重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Example 11] Formulation of the lubricant composition of the present invention (TBN: 7.3 mgKOH / g)
Further, the same formulation as in Example 1 except that 0.3% by weight of an alkali metal borate was added, and 62.2% by weight and 20.7% by weight of base oils A and B were used as base oils, respectively. To prepare a lubricating oil composition.
［実施例１２］本発明の潤滑剤組成物の配合（ＴＢＮ：７．３ｍｇＫＯＨ／ｇ）
分散剤Ｂを分散剤Ａ（添加量：４重量％、窒素量換算添加量：０．０６重量％）に変え、基油Ａと基油Ｂとをそれぞれ６２．２重量％と２０．７重量％用いた以外は実施例１１と同じ配合にて潤滑油組成物を調製した。
[Example 12] Formulation of lubricant composition of the present invention (TBN: 7.3 mgKOH / g)
Dispersant B was changed to dispersant A (addition amount: 4% by weight, addition amount in terms of nitrogen amount: 0.06% by weight), and base oil A and base oil B were respectively 62.2% by weight and 20.7% by weight. A lubricating oil composition was prepared with the same formulation as in Example 11 except that the lubricating oil composition was used.
［比較例１］比較用の潤滑剤組成物の配合（ＴＢＮ：６．６ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ａの代わりに清浄剤Ｆを、添加量：０．９３重量％（硫酸灰分換算添加量：０．４９重量％、有機酸金属塩換算添加量：０．１重量％）にて添加し、基油として、基油Ａと基油Ｂとをそれぞれ６７．１重量％と２２．４重量％用いた以外は実施例１と同じ配合にて潤滑油組成物を調製した。
[Comparative Example 1] Formulation of a lubricant composition for comparison (TBN: 6.6 mgKOH / g)
As a metal-based detergent, detergent F instead of detergent A, an addition amount: 0.93% by weight (addition amount of sulfated ash: 0.49% by weight, addition amount of organic acid metal salt: 0.1% by weight) %), And lubricating oil compositions were prepared in the same manner as in Example 1 except that 67.1 wt% and 22.4 wt% of base oil A and base oil B were used as base oils, respectively. did.
［参考例１］潤滑剤組成物（高硫酸灰分、高リン、高硫黄）の配合
（ＴＢＮ：１３．０ｍｇＫＯＨ／ｇ）
分散剤Ｂの添加量を２．８重量％（窒素量換算添加量：０．０４重量％）そして、分散剤Ｃの添加量を２．４重量％（窒素量換算添加量：０．０２重量％）に変え、金属系清浄剤として、清浄剤Ｄを、添加量：１．８重量％（硫酸灰分換算添加量：０．１４重量％、有機酸金属塩換算添加量：０．８重量％）にて、そして清浄剤Ｈを、添加量：４．６重量％（硫酸灰分換算添加量：１．４３重量％、有機酸金属塩換算添加量：１．８重量％）にて添加し、ＺｎＤＴＰをリン量換算で０．１２重量％、ＶＩＩを５．２重量％、ＰＰＤを０．３重量％添加し、基油として基油Ｃを単独で８２．４重量％用いて潤滑油組成物を調製した。
[Reference Example 1] Formulation of lubricant composition (high sulfated ash, high phosphorus, high sulfur) (TBN: 13.0 mgKOH / g)
The addition amount of dispersant B was 2.8% by weight (addition amount in terms of nitrogen: 0.04% by weight), and the addition amount of dispersant C was 2.4% by weight (addition amount in terms of nitrogen amount: 0.02% by weight). %), And as a metal-based detergent, a detergent D was added in an amount of 1.8% by weight (addition amount in terms of sulfated ash: 0.14% by weight, addition amount in terms of organic acid metal salt: 0.8% by weight). ) And the detergent H was added in an amount of 4.6% by weight (addition amount in terms of sulfated ash: 1.43% by weight, addition amount in terms of organic acid metal salt: 1.8% by weight), Lubricating oil composition containing ZnDTP in an amount of 0.12% by weight in terms of phosphorus, 5.2% by weight of VII and 0.3% by weight of PPD, and using solely 82.4% by weight of base oil C as a base oil. Was prepared.
［参考例２］潤滑剤組成物（高硫酸灰分、高リン、高硫黄）の配合
（ＴＢＮ：１２．８ｍｇＫＯＨ／ｇ）
金属系清浄剤として、清浄剤Ｄを、添加量：１．８重量％（硫酸灰分換算添加量：０．１４重量％、有機酸金属塩換算添加量：０．８重量％）、清浄剤Ｅを、添加量：１．１重量％（硫酸灰分換算添加量：０．４８重量％、有機酸金属塩換算添加量：０．２重量％）にて、そして清浄剤Ｈを、添加量：３．０重量％（硫酸灰分換算添加量：０．９５重量％、有機酸金属塩換算添加量：１．２重量％）にて添加し、基油として基油Ｃを単独で８１．９重量％用いた以外は参考例１と同じ配合にて潤滑油組成物を調製した。
[Reference Example 2] Formulation of lubricant composition (high sulfated ash, high phosphorus, high sulfur) (TBN: 12.8 mgKOH / g)
Detergent D was added as a metal-based detergent in an amount of 1.8% by weight (addition amount in terms of sulfated ash: 0.14% by weight, addition amount in terms of organic acid metal salt: 0.8% by weight), detergent E At an addition amount of 1.1% by weight (addition amount of sulfated ash: 0.48% by weight, addition amount of organic acid metal salt: 0.2% by weight), and detergent H at an addition amount of 3 0.0% by weight (addition amount in terms of sulfated ash: 0.95% by weight, addition amount in terms of organic acid metal salt: 1.2% by weight), and base oil C alone as a base oil was 81.9% by weight. A lubricating oil composition was prepared in the same formulation as in Reference Example 1 except that it was used.
［参考例３］ 市販潤滑剤組成物（ＴＢＮ：１２．１ｍｇＫＯＨ／ｇ）
市販の代表的なＡＰＩ−ＣＦのディーゼルエンジン用潤滑剤（１０Ｗ３０）を購入した。
[Reference Example 3] Commercially available lubricant composition (TBN: 12.1 mgKOH / g)
A commercially available API-CF diesel engine lubricant (10W30) was purchased.
表１
［評価試験結果］
────────────────────────────────────
試験用 硫酸灰分 リン含量 硫黄含量 塩素含量 石鹸分 テスト評点
潤滑油 (wt.%) (wt.%) (wt.%) (ｐｐｍ) (wt.%) ２９０℃ ３００℃
────────────────────────────────────
実施例１ ０．６ ０．０３ ０．０８ ＜５ ２．５ ８．５ ４．５
実施例２ ０．６ ０．０３ ０．０７ ＜５ ０．７ ７．０ ３．５
実施例３ ０．６ ０．０３ ０．０７ ＜５ ０．４ ７．０ ６．０
実施例４ ０．６ ０．０３ ０．０８ ＜５ ２．３ ８．５ ５．５
実施例５ ０．６ ０．０３ ０．２５ ４０ ２．９ ７．５ ６．５
実施例６ ０．６ ０．０３ ０．０９ ＜５ ０．２ ６．５ ５．５
実施例７ ０．６ ０．０３ ０．０８ ＜５ ２．４ ８．５ ６．０
実施例８ ０．６ ０．０３ ０．１１ ＜５ ２．３ ８．５ ５．５
実施例９ ０．６ ０．０３ ０．１０ １０ ２．５ ８．５ ６．０
実施例10 ０．６ ０．０３ ０．０８ ＜５ ２．５ ８．５ ６．０
実施例11 ０．65 ０．０３ ０．０８ ＜５ ２．５ ９．０ ８．５
実施例12 ０．65 ０．０３ ０．０８ ＜５ ２．５ ８．０ ７．０
────────────────────────────────────
比較例１ ０．６ ０．０３ ０．０９ ＜５ ０．１ ５．５ ３．０
────────────────────────────────────
参考例１ １．８ ０．１２ ０．６５ ２０ ２．６ ７．０ ６．０
参考例２ １．８ ０．１２ ０．６２ ２０ ２．２ ６．５ ６．５
参考例３ １．７ ０．１１ ０．５４ １２０ − ７．５ ６．０
────────────────────────────────────
Table 1
[Evaluation test results]
────────────────────────────────────
Test sulfated ash phosphorus content sulfur content chlorine content soap content test score
Lubricating oil (wt.%) (Wt.%) (Wt.%) (Ppm) (wt.%) 290 ℃ 300 ℃
────────────────────────────────────
Example 1 0.6 0.03 0.08 <5 2.5 8.5 4.5
Example 2 0.6 0.03 0.07 <5 0.7 7.0 3.5
Example 3 0.6 0.03 0.07 <5 0.4 7.0 6.0
Example 4 0.6 0.03 0.08 <5 2.3 8.5 5.5 5.5
Example 5 0.6 0.03 0.25 40 2.9 7.5 6.5 6.5
Example 6 0.6 0.03 0.09 <5 0.2 6.5 5.5
Example 7 0.6 0.03 0.08 <5 2.4 8.5 6.0
Example 8 0.6 0.03 0.11 <5 2.3 8.5 5.5 5.5
Example 9 0.6 0.03 0.10 10 2.5 8.5 6.0
Example 10 0.6 0.03 0.08 <5 2.5 8.5 6.0
Example 11 0.65 0.03 0.08 <5 2.5 9.0 8.5
Example 12 0.65 0.03 0.08 <5 2.5 8.0 7.0
────────────────────────────────────
Comparative Example 1 0.6 0.03 0.09 <5 0.1 5.5 3.0
────────────────────────────────────
Reference Example 1 1.8 0.12 0.65 20 2.6 7.0 6.0
Reference Example 2 1.8 0.12 0.62 20 2.2 6.5 6.5
Reference Example 3 1.7 0.11 0.54 120-7.5 6.0
────────────────────────────────────
上記の評価試験結果から明らかなように、本発明の潤滑油組成物（実施例１乃至１２）は、低硫酸灰分含量、低リン含量、かつ低硫黄含量であるにもかかわらず、現在一般的に利用されている高硫酸灰分、高リン含量かつ高硫黄含量のディーゼルエンジン油（参考例１乃至３）と同等もしくはそれ以上の高温清浄性を示している。
As is clear from the above evaluation test results, the lubricating oil compositions of the present invention (Examples 1 to 12) have a low content of sulfated ash, a low phosphorus content, and a low sulfur content. It shows high-temperature detergency equivalent to or higher than that of high-sulfated ash, high-phosphorus-content, and high-sulfur content diesel engine oils (Reference Examples 1 to 3) which are used in the present invention.
Claims (13)
ａ）アルケニルもしくはアルキルこはく酸イミドあるいはその誘導体である無灰性分散剤が窒素含有量換算値で０．０１〜０．３重量％、
ｂ）硫黄含有量が３％以下で全塩基価１０〜３５０ｍｇＫＯＨ／ｇの金属含有清浄剤が硫酸灰分換算値で０．１〜１重量％、
ｃ）ジアルキルジチオリン酸亜鉛が、リン含有量換算値で０．０１〜０．１重量％、そして
ｄ）酸化防止性のフェノール化合物および／または酸化防止性のアミン化合物が０．０１〜５重量％、
の量にて溶解もしくは分散されていて、組成物の全重量に基づき、硫酸灰分量が０．１〜１重量％の範囲、リン含有量が０．０１〜０．１重量％の範囲、そして硫黄含有量が０．０１〜０．３重量％の範囲にあって、塩素含有量が４０ｐｐｍ以下であり、さらに金属含有清浄剤に含まれる有機酸金属塩が組成物中に０．２〜７重量％存在することを特徴とする潤滑油組成物。 In a base oil of mineral oil and / or synthetic oil with a sulfur content of 0.1% by weight or less, at least based on the total weight of the composition,
a) An ashless dispersant which is an alkenyl or alkyl succinimide or a derivative thereof contains 0.01 to 0.3% by weight in terms of nitrogen content;
b) 0.1 to 1% by weight of a metal-containing detergent having a sulfur content of 3% or less and a total base number of 10 to 350 mgKOH / g in terms of sulfated ash content;
c) 0.01 to 0.1% by weight of a zinc dialkyldithiophosphate in terms of phosphorus content, and d) 0.01 to 5% by weight of an antioxidant phenol compound and / or an antioxidant amine compound. ,
Wherein the amount of sulfated ash ranges from 0.1 to 1% by weight, the phosphorus content ranges from 0.01 to 0.1% by weight, based on the total weight of the composition, and The sulfur content is in the range of 0.01 to 0.3% by weight, the chlorine content is 40 ppm or less, and the organic acid metal salt contained in the metal-containing detergent contains 0.2 to 7 in the composition. A lubricating oil composition characterized by being present in a weight percent.
The lubricating oil composition according to any one of claims 1 to 12, which is a multi-grade engine oil further containing a viscosity index improver.
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